Process of reacting acid derivatives with specified organomagnesium chlorides



United States Patent F PROCESS OF REACTING ACID DERIVATIVES WITH SPECIFIED ORGANOMAGNESIUM 'CHLORIDES Hugh E.Ramsden, Metuchen, N. 1., assignor to Metal & Thermit Corporation, New York, N. Y., a corporation of New Jersey No Drawing. Application November 28, 1955 Serial No. 549,543

6 Claims. (Cl. 260-295) This invention relates to a process of reacting organomagnesium chlorides with acid derivatives including esters, diesters, acyl halides, nitriles, cyanogen halides, and orthoesters and to products made by this process. This application is a continuation-in-part of application S. N. 520,141, filed July 5, 1955, now abandoned.

, 2,873,275 Patented Feb. 10, 1959 ICC p-electrons. Expressed in another fashion, the oxygen of the heterocyclic ring structure must be such that electrons of the oxygen atom are available for coordination and complex formation with magnesium. Since Q also apparently functions as a solvent, a Q which has a high melting point may still function in this invention, but

if it is used as solvent, obviously the high melting point tetrahydrofuran, tetrahydropyran, dihydropyran, etc. It

The organomagnesium chloride reagents employed in i H- practicing this invention may be described as RMgCl nQ where R is an aryl group, a vinyl group or a heterocyclic group, as more particularly defined below, n is an inder terminate number from 1 to 3, and Q has the significance hereinafter defined. These organomagnesium chloride reagents are made by reacting the. corresponding RC1 with magnesiumin the presence of compound Q as reaction medium. In accordance with this invention, these organomagnesium chloride reagents are, reacted with acid derivatives including esters and, diesters, acyl halides, nitriles and orthoestersto yield, after further reaction with water or dilute acid, substituted alcohols, ketones, aldehydes, or acetals. These are useful as intermediates for the manufacture of plasticizers, as insecticides, as perfumes and in other products or the alcohols may be converted to olefins useful as polymerization monomers.

Compound Q is a substituted or unsubstituted heterocyclic compound (having 5 or 6 atomsin the ring) con taining one oxygen atom in the ring structure; the other ring atoms being carbon with the exception that one nitrogen atom may be substituted for any carbon atom other than those carbon atoms adjacent to the oxygen. The heterocyclic compounds may contain a single unsaturated bond, as in dihydropyran. Compounds within this definition include tetrahydrofuran, tetrahydropyran, Z-methyltetrahydrofuran, Z-ethoxytetrahydropyran, tetrahydrofurfuryl ethyl ether, dihydropyran, dibenzofuran and N-methylmorpholine. Permissible substitutions being groups which are not reactive with organomagnesium chlorides, or with any of the other components and products of the reaction mixtures of the present process, and includes substituted and unsubstituted alkyl, aryl, alkoxy and aryloxy groups (all allowable substitutes being those unreactive to other components of the reaction mixture as specified hereinbefore). Where nitrogen replaces a carbon atom, hydrogen on the nitrogen atom must be substituted with a group unreactive to the nitriles, and orthoesters to yield useful products.

may also be a 5 or 6 member heterocyclic compound containing one oxygen in the ring and further substituted by monovalent groups and having said characteristics, e. g., Z-methyltetrahydrofuran, Z-ethoxytetrahydrofuran, tetrahydrofurfuryl ethyl ether, N-methyl morpholine, etc. Furthermore, the compound Q may be a 5' or 6 member heterocyclic compound having one oxygen atom in the ring and substituted by polyvalent radicals to form fused ring compounds, providing'that the compound has the necessary characteristics set forth above in. the definition of compound Q, e. g., dibenzofuran, etc.

It is an object of the present invention to provide a process for reacting said organomagnesium chlorides with acid derivatives including esters and diesters, acyl halides, It is also an object of this invention to provide several new products useful in industry. 7

The reactions are carried out in the cyclic tetraor pentamethylene oxide compound, Q, as reaction medium, preferably at a temperature between room temperature and the reflux temperature. However, the temperature is not critical and may be even lower than room tempera ture. Inert hydrocarbon solvents 'may also be used as the reaction medium in place of compound Q. When thereaction between the above-mentioned acid derivatives reactants or reaction products. A further requirement for Q is that the oxygen must be available for electron donation, i, e., the free p-electrons present on the oxygen should be available for coordination with the organomagnesium chloride. Any large blocking groups in the 2 and 5(6) position may restrict the availability of these a esters in accordance with this invention may be illusand the organomagnesium chloride reagent is finished, cold water or dilute acid is added carefully and the resulting substituted alcohol, aldehyde, ketone or acetal is recovered by distillation or otherwise.- The sequence of reactions in the case ofesters is illustrated by the following general equations:

For acyl halides, the general reaction may be written: (1A) RMgCl-nQ+RCOX- RRCOIMgClX+nQ RR'CO then reacts according to Equations 2 and 3.

For nitriles, the general reactions are:

For orthoesters, the general reaction is:

(1C) RMgCl -nQ+R"'C(OR' RRC(OR') +nQ X is a halogen and R, R and R are organic'radicals which will be more specifically defined in what follows i and R" may be ARYLMAGNESIUM CHLORIDE REAGENTS (A) Reactions with esters The reactions of arylma gnesium chloride reagents with trated by the following over-all equations, which include the hydrolysis step (Equation 3 above) though it must be understood that this step is carried out separately.

wherein n is a small whole number, R and R may be alkyl, aryl, alkenyl, and aralkyl, and wherein R is defined as:

Ra Rn wherein R, R R, R and R may be the same or different substituents as long as they do not react with the arylmagnesium chloride reagent. They may be hydrogen; fiuorine, chlorine; alkyl, such as methyl, ethyl, etc.; alkenyl, such as vinyl, allyl, propenyl, etc.; aryl, such as phenyl, tolyl, xylyl, Xenyl, etc.; aralkyl, such as benzyl, phenylethyl, cinnamyl, methylbenzyl, etc.; heterocyclic, such as thienyl, thenyl, furyl, etc.; alkoxy, such as methoxy, ethoxy; allyloxy, etc.; aryloxy, such as phenoxy, tolyloxy, Xenyloxy, etc.; and dialkylamino, such as dimethylamino, diethylamino, etc. groups.

Arylmagnesium chlorides react with di, tri-, and polyesters to form intermediates which may be isolated (shown in brackets) as Well as to form end products, according to the following reactions:

7a OMgCl 0M 01 MgClmQ I g OMgCl molv'coa wherein R and R arerthe same as in Reactions 4 through 6, and R" is a divalent radical inert to organornagnesium chloride reagents.

Alcohols may be dehydrated to yield desirable olefins, or diolefins in the case of diesters products. Triand polyesters function similarly to give their accompanying olefins, the requirement being presence of hydrogens on carbons a to the OH group.

chlorophenyl and substituted chlorophenylmagnesinm chlorides react with monoesters, such as those of monobasic carboxylic acids according to Reactions 4 through 6, wherein R and R" are monovalent organic radicals free: of groups reactive to RMgCl, and R is defined in this case as:

Q, m g n;

Cl C1 C1 C1 C1 C1 C1 01 Cl C1 C1 G1 C1 O1 C1 C1 O1 O1 G1 C1 C1 C1 G1 G1 Cl Cl 01 Cl Cl 01 C1 C1 C1 C1 C1 C1 In the above radicals any positions not containing chlorine may be filled with fluorine or any organic monovalent group such as alkyl, alkenyl, aryl, dialkylamino, alkoxy, aryloxy and alkenyloxy groups in place of the hydrogen. In addition, divalent groups such as alkylidene dioxy groups may join to adjacent open positions. The substituents may contain functional groups if these are not reactive to the arylmagnesium chloride reagent.

Where R COHR', the product of Reaction 6, contains the group R COHCH=R COHR may be dehydrated to yield further products: R C=C=.

. chlorophenyl and substituted chlorophenyl magnesium chloride reagents further react with diand polyesters such as those of diand polycarboxylic organic acids, according to Reactions 7 through 7e. In this case, R and R" are the same as defined for Reactions 7 through 7e. R in this case is the chlorophenyl or substituted chlorophenyl as defined above for monoester reactions.

Wherever the group R COHCH= occurs in the chlorophenyl reactions, dehydration may yield desirable com pounds, as for example:

Xenylmagnesium chlorides will react with esters of monocarboxylic acids:

wherein R, R", R' and R"" are monovalent organic radicals inert to RMgCl.

R may be defined in the above reactions as a xenyl radical, substitutedor unsubstituted. The raw materials for preparing the RMgCl by the polymethylene oxide process might also contain some chlorinated terphenyls.

Thus, R may be:

Ch gch Ola The bond to the magnesium may be ortho, meta or para. Other groups may be present instead of ring hydrogen, including alkyl, alkenyl, aryl, alkaryi, aralkyl,

ilk,

Ola

fluorine, alkoxy, alkenoxy, aryloxy, dialkylamino, etc. groups. 3

Xenylmagnesium chlorides react also with esters of polycarboxylic acids according to Reactions 7-7e, R and R" being as defined for these reactions and R being as defined for Reactions 4a and 5a.

Bifunctional arylene di(magnesium chloride) reagents may also be used with monoesters to form mono-addition products as well as polymers, according to the following reactions:

RMEODMQ R'omG where the hydrogens on the ring may be replaced by any group not reactive to RMgCl, such as chlorine, fluorine, R' N-, R'O-, R, etc., and where R is a monovalent organic radical. Two neighboring R radicals may be cyclicized.

R(MgC1) may also be:

(MgCl): where hydrogen may be replaced as above;

(MgCD where hydrogen may be replaced as above;

(MgCl) where hydrogen may be replaced as above;

(MgClhz where hydrogen. may be: replaced. as; aboveaor RCfOH-GH: groups present, may also be dehydrated to yielddesirable compounds according to Reaction 8. Y

(B) Reactions with-acyl halides Arylmagnesium chloride reagents react with 'acyl halides by the'following overall equations which include the hydrolysis step (Equations 3);. it is to be understood that the-latter reaction is carried out separately:

RzCOHCHi RgO=CH may; react, with nitriles, to, form'zketonca after: hydrolysis,,

The reactions are as follows:

RM Cl-n RON g Q B O RR'C=NMgCl RR'O=O:+ nX Symmetrical ketones are prepared by the following scheme:

26 RMgCl RMgCl-nQ oloN RON H+,H',o R2C=NMgC1 R,o=o +..1;Q where R is a monovalent organic radical inert to RMgCl, and wherein R is defined as in Reactions 4 through 6,

Xenylrnagnesium chloridessimilarly react with ,nitriles, according to Reactions 25- and 26, wherein R is defined as above, and R is the sameas defined'in Reactions 4a, 5a and 9through 12;.

Chlorophenyl and substituted chlorophenyl magnesium chlorides react with nitriles according to Reactions 25 and 26, wherein R is defined as above, and'R is chlorophenyl as defined for Reactions 4 through 6.

Arylmagnesium chlorides, including Xenyl and chlorophenylmagnesium chlorides, as defined for Reactions 4-6, 4a, 5a and" 9-12, react with compounds having more than one nitrile group as follows:

2RMgCl-nQ+R"(CN): R"(RCNMgCl)z nQ lid-[H10 I n 'moon wherein R is a monovalent hydrocarbon radical such as cal carrying functional groups inert to RMgCl-nQ, R! is a divalent aliphatic or aromatic hydrocarbon radical or such a hydrocarbon radical carrying functional groups inert to RMgCl-nQ, X is chlorine, bromine or iodine, and R is defined as in Reactions 4 through 6. I

Chlorophenyl and substituted chlorophenylmagnesium chlorides react with acyl halides according to Reactions 20-2311. In this case, R is the chlorophenyl radical as previously defined for Reactions 4 through 6. v

Xenylmagnesium chlorides similarly react with acyl halides according to Reactions 2'0-23a. R in this case is the xenyl radical as previously defined for Reactions 4a, 5a and 9 through 12.

Bifunctional arylene di(magnesium chloride) reagents also react with acyl halides, acc'ordingto the'following:

wherein R and R are the same as defined for Reactions 14 through 18. They react also with esters of polycarboxylic acids to yield complex products.

C. Reactions with nitriles dehydrate l RzC==CHR-CH=C R2 Bifunctional arylene di(magnesium chloride) reagents also react with nitriles as follows:

Aldehydes and ketones including-those ordinarily ditficult to prepare, may be preparedas acetals and ketals by the reaction of arylmagnesium chloride reagents with orthoformates and orthoesters as follows:

wherein R, R and R are the same as in Reactions 4, 5 p

and 6.

Chlorophenyl and substituted chlorophenyl -magnesium chlorides react with. orthoformates and orthoesters as fol- 9 and generally according to Reaction 30, wherein R, R and R" are the same as defined for Reactions 4, 5, and 6 using chlorophenyl in (A) of Arylmagnesium Chloride Reagents.

Xenylrnagnesium chlorides react with orthoformates and orthoesters according to Reactions 29 and 30. In this case R, R and R are the same as in Reactions 4a, 5a and 9 through 12.

Bifunctional arylene di(magnesiurn chloride) reagents react with orthoformates and orthoesters as follows:

(32) R(MgCl) -nQ+CH(OR') (33) R(MgC1) -nQ-l-R"C(OR') R[R"C(OR' )2]3+nQ wherein R(MgCl) R and R are the same as in Reactions 14 through 19.

HETEROCYCLICMAGNESIUM CHLORIDE REAGENTS (A) Reactions with esters Heterocyclicmagnesium chloride reagents, RMgCl'nQ, as defined below, react with esters of monobasic carboxylic acids generally according to the following reactions:

oxidation RMgCl-nQ +R'OzCH [ROHO] R2CHOH in which n is a small whole number, Qis as previously defined, and R isa radical which includes in its structure an oxygen, sulfur or tertiary nitrogen heterocycle, its bond to magnesium being through a carbon of an aromatic or pseudoaromatic ring.

Among the types of heterocyclic groups, R, which may be employed in reactions such as Nos. 34-36 are those shown in the following structural formulas in which a free bond indicates the point of attachment of the MgCl group except that when two free bonds are shown in one structure they represent alternative points of attachment. In these structures any or all hydrogens in the molecules may be replaced by fluorine, chlorine, alkyl, alkenyl, aryl, alkoxy, aryloxy or other groups not reactive to RMgCl. Two adjacent substituents may be linked or cyclized to form further condensed rings.

(ill Q:

15 0 N W N ,r, g, ,t,

Fur'yl NR' pyrryl N--R' indolyl I? [I C o o o N Benzofuryl Dibenzofuryl N.Rim1dazolyl N N N ,0 l l l l l 1;: o o N R! Benzlrnidazolyl Oxazolyl Benzoxazolyl Pyrlmidyl is) L Benzopyri midyl Thiazolyl Benzothiazolyl Triazinyls Pyrazinyl Pyridazinyl 5 The reactions with esters of polycarboxylic acids are the following:

S MgC1-nQ.+ CaHr-OzG-CHiCHaCOrGxHI I)cmomowmgon-(H s =o(on)onion c o i s v S a dehydrate C=CHCH=C s A i wherein R is a monovalent organic radical and R" is a divalent organic radical, both R and R being nert to RMgCl. R is a heterocyclic radical as described for Reactions 34 through 36.

(B) Reactions with acyl halides Heterocyclic magnesium chloride reagents RMgCI-nQ, react with acyl halides according to Reactions 20-2311 in which Rand R" have the meanings given them for those equations while R is'defined as for Reactions 34-36.

(C) Reaction with nitriles Heterocyclic magnesium chloride reagents, RMgCl-nQ, as defined above, react with nitriles as in Reactions 25 and An interesting special case is the reaction with acrylonitrile which proceeds by either of the follow ng reactions depending upon the reaction conditions:

an el-no om-one ao o on=om M) Romaine: nQ

D) Reaction with orthoesters v :HCtCl'OCYCliC magnesium chloride reagents,.RMgCl-nQ,

as defined above, react with orthoformates and orthoesters according to Reactions 29 and 30. r

VINYL MAGNESIUM CHLORIDE REAGENTS In this application, the term vinyl radical refers to the vinyl group or to substituted vinyl groups. Thus, a vinyl chloridevhas the general formula:

where R, R and R',may be thetsame or different and may-be hydrogen or any hydrocarbon group, aliphatic or aromatic; they may also be hydrocarbon groups with functional group substituents provided that the latter are inert to magnesium and to vinyl magnesium chloride; R may cyclize with R" or R as, for example, in the compound furthermore, R may also be chlorine, in which case the magnesium may react with one or both chlorincs.

When the formula RMgCl-nQ is used in this application to refer to a vinyl magnesium chloride, then R represents the group where R, R and R' are as defined above.

Similarly, in a vinyl di(magnesium chloride) reagent, R(MgCl) -nQ, R represents the bivalent group (A) Reaction with esters Vinyl magnesium chloride reagents, RMgCl-nQ, as 'definedabove react with monoesters in accordance with Reactions 1-3 and 4-6 and with polyestersin accordance with Reactions 7-7e in which R and R" are defined as they were forthe se equations;

(B) Reactions with acyl halides Vinyl magnesium chloride reagents, RMgCl-vnQ, as defined above, react with acyl halides forming vinyl ketones or divinyl alcohols which may be dehydrated provided tx hydrogens are present to yield triolefins as follows (shown for vinyl-magnesium chloride complex):

dehydrate wherein X is halogen and R, R and R' are monovalent radicals inert to vinyl magnesium chloride,

13 (C) Reactions with nitriles Vinyl magnesium chloride reagents, RMgCl-nQ, as defined above, react with nitriles to form vinyl ketones as follows:

wherein R is defined as a monovalent organic radical inert to vinyl magnesium chloride.

(E) Reactions of vinyl di(magnesium chloride) reagents Vinyl di(magnesium chloride) reagents, R(MgCl) -nQ, as defined above react with monoesters, polyesters, acyl halides, nitriles and orthoestersby reactions analogous to those described for bifunctional arylene di(magnesium chloride) I reagents, namely Reactions 14-19, 24, 27, 28, 32 and 33.

The following examples are further illustrative of the present invention. It is to be understood, however, that the invention is not restricted to the specific embodiments described herein in detail.

EXAMPLE 1.-'-PREPARATIQN OF 3,5-DIVINYL-3,5-DIHY- DROXYHEPTADIENE-LB Two moles of vinylmagnesium chloride-tetrahydrofuran complex in tetrahydrofuran solution (700 ml.) were introduced into a 2 liter, 3 neck flask equipped with a stainless steel stirrer, a chopping burette and a reflux condenser. Air was displaced from the apparatus by dry nitrogen. 72.2 grams (0.45 mole) of methyl malonate were added through the dropping funnel over a twenty minute period, the reaction mixture being stirred meanwhile. The temperature was held between 20 and 30 C. during the addition by means of an ice bath. Reaction continued slowly thereafter. A color test made the next morning indicated that much of vinylmagnesium chloride reagent was still present. After another day, however, the test was only weakly positive and the batch was then cooled to C. and hydrolysed by dilute hydrochloric acid. The batch now formed two clear liquid layers which were separated in a separatory funnel. The aqueous portion was extracted with ethylether, the extracts being added to the organic portion. Ethyl ether, and tetrahydrofuran were stripped from the organic por tion. From the residue remaining, 36 grams 3,5-diviny1- 3,5-dihydroxyheptadiene-1,6 were recovered as a fraction boiling at 90-93 C. at mm. pressure. Its refractive index was 1.4145 27.

EXAMPLE 2.PREPARATION OF 3,6-DIVINYL-3,6-D1HY- DROXYOCTADIENE-1,7

A solution of 1.88 moles of vinylmagnesium chloride complex in tetrahydrofuran was allowed to react with 0.45 mole of ethyl succinate by the procedure of Example l. The product was hydrolysed by dilute hydrochloric acid. The organic layer thus formed was stripped of solvent to yield a crude 3,6-divinyl-3,6-dihydroxyoctadiene-l,7. When purification of the latter was attempted by vacuum distillation, it polymerized rapidly.

EXAMPLE 3 Crude o-phenylene bis(divinyl carbinolll was made by the reaction of 1.95 moles of vinylmagnesium chloride complex in tetrahydrofuran with 0.45 mole of ethyl phthalate using the procedure of Example 2. In an attempt to purify the product by vacuum distillation, it polymerized.

EXAMPLE 4.-PREPARATION OF ACROLEIN EXAMPLE 5.PREPARATION OF 1,4-PENTADIEN-3-OL Two moles of vinylmagnesium chloride-tetrahydrofuran complex in 700 ml. of tetrahydrofuran is placed in a 2 l. flask as described in Example 1, and 1 mole of methyl 'formate added dropwise over a 20 minute period. The temperature of the addition is kept between 20-30 C., After refluxing 1 hour, dilute sulfuric acid is added to effect hydrolysis, and the two layers separated. The aqueous layer is extracted with ether and the ether extracts added to the organic layer. moved and from the residue there is obtained 1,4-pentadien-3-ol.

EXAMPLE 6.PREPARATION OF 3-1\i[ETHYL-1,4-PENTA- The apparatus of Example 1 is used and 1 mole of ethyl acetate is added dropwise over a twenty minute period to a stirred solution of 2 moles of vinylmagnesium chloride-tetrahydrofuran complex in 700 ml. tetrahydrofuran. An ice bath is used to keep the temperature between 20 and 30 C. The reaction mixture is then brought to the boiling point and allowed to reflux for 1 hour. It is next cooled, hydrolyzed with dilute hydrochloric acid, the two layers separated and the water layer extracted with ether. The combined organic layer and ether extracts is stripped of solvent and the residue purified. This gives 3-methyl-1,4-pentadien-3-ol.

EXAMPLE 7 .PREPARATION OF 3-UNDECYL-L4- PENTADIEN-3-OL 3-undecyl-1,4-pentadien-3cl is prepared by the procedure of Example 5, using two moles of vinylmagnesium chloride-tetrahydrofuran complex and one mole of butyl laurate as the reactants.

EXAMPLE 8.PREPARATION OF 3-VINYL-1,11-

' EICOSADIEN-3-OL Two moles of vinylmagnesium chloride-tetrahydropyran complex react with 1 mole of methyl oleate under the conditions of Example 6 to yield 3-vinyl-1,11-eicosadien-S-ol.

EXAMPLE 9.PREPARATION OF ETHYL 2-HYDROXY-2- VINYL-3-BUTENOATE Four moles of vinylmagnesium chloride-tetrahydrofuran complex reacts with 1 mole of diethyl oxalate under the conditions of Example 6 to give 3,4-divinyl-3,4- dihydroxy-1,5-hexadiene.

EXAMPLE 11.PREPARATION OF BUTYL it-HYDROXY- 4-VINYL-5-HEXENOATE When 2 moles of vinylmagnesium chloride-tetrahydrofuran complex is caused to react with 1 mole of di-. t butyl succinate according to the process described in Solvent is then re- 15 Example 5, the resulting product is butyl 4-hydroxy-4- vinyl- S-hexenoate.

EXAMPLE 12.PREPARATION OF 3-6-DIVINYL-3,6- DIHYDROXY-1,7-CTADIENE Four moles of vinylmagnesium chloride-tetrahydrofuran complex reacts with 1 mole of dibutyl succinate by the procedure of Example 6 to yield 3,6-divinyl-3,6 dihydroxy-l,7-octadiene.

EXAMPLE 12a.-PREPARATION OF 3,6-D1'VINYL- 1,3,5,7-OCTATETRAENE The compound of Example 12 is dehydrated by refluxing it in glacial acetic acid with a crystal of iodine. The product is 3,6-divinyl-1,3,5,7-octatetraene.

EXAMPLE 13.PREPARATION OF METHYL 6,6-DI- VINYL-G-HYDROXYCAPROATE Dimethyl adipate, 1 mole, and vinylmagnesium chloridetetrahydrofuran complex, '2 moles, react together by theprocedure of Example 5 to form methyl 6,6-divinyl-6- hydroxycaproate.

EXAMPLE 14.PREPARATION OF 3,8-DIVINYL-3,8- DIHYDROXY1,9-DECADIENE Four moles of vinylmagnesium chloride-tetrahydrofuran complex and 1 mole of dimethyl adipate are allowed to react under the conditions of Example 6. The resulting product is 3,8divinyl-3,8-dihydroxy1,9-decadiene.

Dehydration of 3,12-divinyl-3,12-dihydroxy-1,l3-tetra decadiene by the method of Example 12a gives 3,12-

divinyl-],3,l1,13-tetradecatetraene.

EXAMPLE 17.-PREPARATION OF ETHYL 3,4, l-TRI- VINYL--HYDROXYBU'IYRATE Three moles of vinylmagnesium chloride-tetrahydrofuran complex add to 1 mole of diethyl maleate under the conditions of 5 to give ethyl 3,4,4-trivinyl-4- hydroxybutyrate.

EXAMPLE 18.PREPARATION OF ETHYL p- (DIVINYL- HYDROXYMETHYL) BENZOATE The reaction of 2 moles of vinylmagnesium chloridetetrahydrofuran complex with ,1 mole of diethyl terephthalate by the method of Example 6 results in the formation of ethyl p-(divinylhydroxymethyl) benzoate.

EXAMPLE 19.PREPARATION OF p-PHENYLENE BIS (DIVINYLCAEBINOL) p-Phenylene bis(divinylcarbinol) is made by the reaction of 4 moles of vinylmagnesium chloride-tetrahydrofuran complex with 1 mole'of diethyl terephthalate, using the procedure of Example 5.

EXAMPLE 20.PREPARATION OF DIVINYL- IHENYLCARBINOL When 2 moles of vinylmagnesium chloride-tetrahydrofuran complex is allowed toreact with 1 mole of methyl 16 benzoate according to the conditions of Example 6, there is obtained divinylphenylcarbinol.

EXAMPLE 2l.-PREPARATION OF DIVINYL(p-METH- OXYPHENYL) CARB INOL The reaction between 2 moles of vinylmagnesium chloridetetrahydrofuran complex and 1 mole of methyl anisate by the process of Example 5 leads to divinyl(p-methoxyphenyl) carbinol.

EXAMPLE 22.PREPARATION OF DIVINYL (u-FURYL) CARBINOL The conditions of Example 5, using 2 moles of vinylmagnesium chloride-tetrahydrofuran complex and one mole of methyl furoate as reactants are followed. The product isolated is divinyl (a-furyDcarbinol.

EXAMPLE 23.PREPARATION 0F DIVINYL- 3-PYRIDYL) CARBINOL Two moles of vinylmagnesium chloride-tetrahydrofuran complex reacts with 1 mole of methyl nicotinate by the process described in Example 6 to give divinyl(3-pyridyl) carbinol.

EXAMPLE 24.PREPARATION OF DIVINYL(2,4- DICHLOROPHENOXYMETHYL) CARBINOL Two moles of vinylmagnesium chloride-tetrahydrofuran complex reacts with 1 mole of butyl 2,4-dichlorophenoxyacetate under the conditions of Example 5 to yield divinyl(2,4-dichlorophenoxymethyl)carbinol.

EXAMPLE 25.PREPARATION OF METHYL 4-VINYL- 4-HYDROXYVALERATE Equirnolar quantities of vinylmagnesium chloride-tetrahydrofuran complex and methyl levulinate are allowed to react according to Example 6 and there is isolated methyl 4 vinyl-4-hydroxyvalerate.

EXAMPLE 25a.PREPARATION OF METHYL QWVINYL-E-PENTENOATE Dehydration of methyl 4-vinyl-4-hydroxyvalerate b refluxing it in glacial acetic acid with a crystal of iodine leads to methyl 4-vinyl-3- pentenoate.

EXAMPLE 26.PREPARATION OF 3,6-DI'VINYL-3fi- DIHYDROXY-l-HEPTENE 'When 3 moles of vinylmagnesium chloride-tetrahydrofuran complex reacts with 1 mole of methyl levulinate according to Example 5, there is obtained 3,6-divinyl-3,6 dihydroxy-l-heptene.

EXAMPLE 26a.PREPARATION OF 3,6-DIVINYL-1,3,5

' HEPTATRIENE The compound from Example 26 is dehydrated 'by the method of Example 12a and there results 3,6-diviny1-'1,3,5 heptatriene. I

EXAMPLE 27.PREPARATION OF METHYL 4-PENTENOA'1E One mole of vinylmagnesium chloride-tetrahydrofuran complex reacts with 1 mole of methyl acrylate by the process of Example 6, and gives by 1,4-add1tion methyl 4-pentenoate.

EXAMPLE 28.VPREPARATION OF 3-METHYL-L'4- PENTADIENE-3-OL Two moles of vinylmagnesium chloride-tetrahydrofuran complex is allowed to react with 1 mole of acetyl chloride under the conditions of Example 5 to yield 3- methyl-1,4-pentadiene-3-ol.

EXAMPLE 28a.PREPARA'lfION OF Z-YINYL 1,3-BUTADIENE 3 methyl 1,4 pentadiene 3 olis dehydrated by the method of Example 15a and gives 2-vinyl-1,3-butad1ene.

EXAMPLE 29.PREPARATION OF METHYL VINYL KETONE I One mole of vinylmagnesium chloride in 3 moles of tetrahydrofuran is placed in a flask as described in Example l and a suspension of 0.5 mole anhydrous fused zinc chlorid? in 2 moles of tet'rahydrofuran is added wlth we e 17 stirring. The reaction mixture is allowed to reflux 2 hours, then cooled to room temperature. To this is added,

over a period of twenty minutes, one mole of acetyl chloride. An ice-bath is necessary to maintain a tem' perature of 20-30 C. After the addition is complete, the mixture is allowed to reflux two hours, then cooled to room temperature and hydrolyzed with dilute hydrochloric acid. The organic layer is separated, solvent removed and from the residue is isolated methyl viny ketone.

EXAMPLE 30.PREPARATION OF 3-VINYL-3-HYDRQXY- 1,3-HEXADIENE Two moles of vinylmagnesium chloride-tetrahydrofuran complex reacts with 1 mole of butyryl chloride by the method of Example to give 3-vinyl3-hydroxy-1,3- I

hexadiene.

EXAMPLE 31.PREPARATION OF VINYL PROPYL KETONE a The procedure of Example 29 is followed using on mole of vinylmagnesium chloride, 0.5 mole zinc chloride, and 1 mole of butyryl chloride as reactants. In this way there is obtained vinyl propyl ketone.

EXAMPLE 32.PREPARATION OF DIVINYL' PHENYLCARBINOL The reaction of 2 moles of vinylmagnesium chloridetetrahydrofuran complex with 1 mole of benzoyl chloride by the procedure of Example 5 yields divinylphenylcarbinol.

EXAMPLE 33.PREPARATION OF P HENYL VINYL KETONE One mole of vinylmagnesium chloride-tetrahydrofuran complex and 0.5 mole of zinc chloride is allowed to react with 1 mole of benzoyl chloride under the conditions of Example 29 to give phenyl vinyl ketone.

EXAMPLE 34:.PREPARATION OF 3,4-DIVINYIr3,4- 1

DIHYDROXY-l,5-HEXADIENE One mole of oxalyl chloride is added to 4 moles of vinylmagnesium chloride-tetrahydrofuran complex in the manner described in Example 6. From the residue there is isolated 3,4-divinyl-3,4-dihydroxy-1,5-hexadiene.

EXAMPLE 35.--PREPARATION 01+ METHYLENE PYRUVYL CHLORIDE Equimolar quantities of vinylmagnesium chloridetetrahydrofuran complex and oxalyl chloride arerallowed to react in the presence of zinc chloride by the process described in Example 29. No dilute acid is added, however. Instead, the solid is filtered off and the filtrate distilled, giving methylenepyruvyl chloride.

EXAMPLE 36.PREPARATION 0F DIACRYLYL When 2 moles, of vinylmagnesium chloride-tetrahydrofuran complex and 1 mole of zinc chloride is allowed to react with 1 mole of oxalyl chloride, there is obtained diacrylyl.

EXAMPLE 37.PREPARATION OF ETHYL fi-ACRYLYLPROPIONATE Equimolar quantities of vinylmagnesium chloride-tetrahydrofuran complex and the acid chloride of monoethyl succinate are allowed to react in the manner described in Example 29 (0.5 mole of zinc chloride present) to yield ethyl fl-acrylylpropionate.

EXAMPLE 38.--PREPARATION OF 3,6-DIHYDROXY- LT-OCTADIENE One mole of the acid chloride of monoethyl succinate is added to 4 molesof vinylmagnesium chloride-tetrahydrofuran complex according to Example 6 and the resulting product is 3,6-dihydroxy-l,7 octadiene.

EXAMPLE 39.-PREPARATION 0F. 8-ACRYLYLVALERYL CHLORIDE Oneniole of vinylrnagnesium chloride-tetrahydrof uran complex and 0.5 mole of zinc chloride is allowed to react r 18 with 1 mole of adipoyldichloride in the manner described in Example 29 to give 8-acrylylvaleryl chloride.

7 EXAMPLE 40.PREPARATION OF IA-DIACRYLYL- BUTANE When 2 moles of vinylmagnesium chloride, 1 mole of zinc chloride and 1 mole of adipoyldichloride are caused to react under the conditions of Example 29, there is obtained ,l,4-diacrylylbutane.

The conditions of Example 29 are followed using as reactants 1 mole of vinylmagnesium chloride-tetrahydrofuran'complex (0.5 mole zinc chloride present) and 1 mole of a-furoyl chloride. The resulting product is vinyl ,u-furyl ketone.

EXAMPLE 43.PREPARATION OF DIVINYL wFURYLmARBINOL Two moles of vinylmagnesium chloride-tetrahydrw furan complex react with 1 mole of a-fur'oyl chloride in the manner described in Example 6 to give divinyl (a-furyl) carbinol.

' EXAMPLE Hr-PREPARATION OF METHYL VINYL KETONE ,Equimola r quantities of vinylmagnesium chloride 'tetrahydrofuran-complex and acetonitrile react by the process of Example 5 and there is obtained methyl vinyl ketone.

EXAMPLE 45.PREPARATION OF VINYL PROPYL KETONE One mole of vinylmagnesium chloride-tetrahydrofuran complex is allowedto react with 1 mole of butyronitrile according to the procedure of Example 6 to yield vinyl propyl ketone.

EXAMPLE 46.PREPARATION 0F PHENYL VINYL KETONE Phenyl vinyl ketone is prepared by the reaction of 1 mole each'of vinylmagnesium chloride-tetrahydrofuran complex and benzonitrile under the conditions of Example 5.

EXAMPLE 47.-PREPARATION 0F P-VINYL- PROPIONITRILE One mole of vinylmagnesium chloride-tetrahydrofuran complex reacts with-1 mole of acrylonitrile according to the procedure of Example 6. 1,4-addition'occurs'primarily, giving fi-vinylpropionitrile. I

EXAMPLE 48.-PREPARATION OF 2-VINYL- SUCCINONITRILE When 1 mole of vinylmagnesium chloride-tetrahydrofuran complex is added to 2 moles of :fumaronitrile by thQPIOCCSS of Example 6, the resulting product is 2- vinylsuccinonitrile.

' EXAMPLE 49.-PREPARATION or fl-vmrn B-ACRYL'YLPROPIONITRILE The reaction of 2 moles of vinylmagnesiurn chloridetetrahydrofuran complex and 1 mole of fumaronitrile uuderthe conditions of Example 5 leads to p-vinylacrylylpropionitrile.

assass n EXAMPLE ed-mmmnarton 'on nnnzxnnnmnm I One mole of phenylmagnesium chloride-tetrahydrofuran complex is added .to a stirred solution of 4 moles of methyl formate in tetrahydrofuran in the manner described in Example 5. When the organic layer is worked up, there is obtained as the final product, benzaldehyde, B. P. 179 C.

EXAMPLE 51.-PREPARATION OF'BENZHVYDROL When '1 mole "of methyl form'ate is added to 2 moles of phenylmagnesium chloride-tetrahydrofuran complex under the conditions of Example .6, the resulting product is benzhydrol, M. P. 68-9 C. I

EXAMPLE 52.PREPA'RATION OF LDIPHENYL- METHYLCARBINOL The reaction of 2 moles of phenylmagnesium chloride and 1 mole of ethyl acetate accordingto the process of Example '5 yields diphenylmethylcarbinol.

EXAMPLE '3.'PREPARATION OF 'BUTYL 431-1)]? PHENYL--HYDROXYBUTYRATE Two .moles of phenylmagnesium chlorideetetrahydrofuran complex is allowed to react with 1 mole of dibutyl wsuccinate as described in Example .6, and there is .ob-

tained butyl 4,4-diphenyl-4ehydroxybutyrate.

EXAMPLE :54.-PREPARATION 0F 1,1,6,6-'TETRA-- =PHENYLHEXYLENE GLYCOL-1,6 When 4 moles of phenylmagnesium -'chloride-tetrahydrofuran complex and 1 mole of .dimethyl-adipate are caused to react according to Example 5, the product formed is 1,1g6,6-tetraphenylhexylene -g1ycol-1,6.

EXAMPLE 55.-PREPARATION 0F 1.1.10;-31ETRA- PHENYLDECYLENE GLYCOL-1,1o The reaction between 4 moles of phenylmagnesium chloride-tetrahydrofuran complex and 1 mole of diethyl sebacate is carried out by the process of Example 5, giving 1,1,10,IO-te-traphenyldecylene glycol-1,10. I

EXAMPLE 56=-PREPARATION on .TRIPHENXL- CARBINOL Two moles of phenylmagnesium chloride-tetrahydrofuran complex and 1 mole of methyl benzoate react under the conditions of Example 6 to yield triphenylcarbin01, M. P. 162 C.

EXAMPLE 57.PREPARATION OF .DIPHENYL- (a-FURYL) CARBINOL Diphenyl (a-furyl)carbinol is prepared by allowing 2 moles of phenylmagnesium chloride-tetrahydrofuran complex and l-mole of methyl 'furoate to react in the manner described in Example '5.

EXAMPLE 58.--PREPA'RATION OF 1,'1,4-TRIPH'ENYL- IA-DIHYDROXYPENTANE 'When 3 moles of phenylmagnesium chloride-tetra'hydrofuran complex reacts with 1 mole of methyl levulinate accordingrto Example 15, there is obtained 1,1,4-triphenyl- 1,4-dihydroxypentane.

' EXAMPLE 58a.-- PREPARATION 0F ?1,1,4TRI?HEN.YL-

CLB-PENTADIENE Dehydration of 1,1,4 triphenyl-1,4-dihydroxypentane by refluxing it in benzene with a small quantity of ptoluene-sulfonic acid yields 1,1,4-triphenyl-1,3-pentadiene. EXAMPLE 59.PR-EPARATION OF METHYL e-PHENYLPROPIQNATE One mole of phenylmagnesium chloride=tetrahydrojuran complex reacts with 1 mole of methyl acrylate by the process of Example 6 and gives :by ;1',4-addit;ion methyl fl-phenyhnropionate.

EXAMPLE .60;-.PREP-ARAT'ION on 'PHENYL METHYL KETONE One mole of phenylmagnesium chloride-tetrah-ydro- "furan complex and 0.5 mole of zinc chloride in 3 .mol es of tetrahydrofuran react according to Example 29 with 1 mole of acetyl chloride to yield phenyl methyl ketone.

B1.-4IREEARATION 'OF BENZOPHENOEE I One mole of phenylmagnesium chloride-tetrahydro- 'furan complex and 0.5 .mole of zinc chloride is allowed to react with 1 :mole of benzoyl chloride under the conditions of Example .29 to .give henzophenone, B. P. 3069C.

IEXA'MBLE (ll-PREPARATION OF DIBENZOYL When 2 moles of phenylmagnesium chloride-tetrahydrofuran complex and 1 mole of zinc chloride is allowed to react with 1 mole of oxalyl chloride, by the process of Example 29 there 'is obtained-dibenzoyl, benzil.

EXAMPLE iea- PnmPAn-h'rrolv 0F ETHYL 'B-BENZOYLPROPIONATE Equim'o'l'ar quantities of phenylmagnesium chloridetetrahydrofuran complex and the acid chloride of monoethyl succinate are allowed 'toireact in the manner described in Example '29 (015 mole of-zinc chloride present) to yield :ethyl fl-benzoylpropionate.

EXAMPLE 'es- PREPnrtxlroN 0F ACETOP-HENON E 'One mole of phenylmagnesium chloride-tetrahydrofuran complex reacts with '1 mole of acetonitrile by the process of Example 5 and there 'is obtained acetophenone, B. P. 202 C.

EXAMPLE65.;PREPARATION OE BENZOPHENONE Benzophenone is prepared by the reaction of 1 mole each of phenylmagnesium chlori de-tetrahydrofuran complex and benzonitrile under the conditions of Example 5. It has B. P. 306 C.

EXAMPLE G6.P.REPARATION OF p-CHLOBO- BENZALDEHYDE One mole of p-chlorophenylmagnesium chloride-tetrahydrofu'ran complex .is added to a stirred solution .of 4 moles of methyl formate in tetrahydrofuran in the manner described in Example 5. When the organic layer is worked up, there is obtained as the final product, pchlorobenzaldehyde, B. P. 21 4 C., M. P. 47 C.

EXAMPLE 6'7.'PREPARATION OF DI(p-'CHLORO- PHENYL) CARBINOL When l mole of methyl formate is added to 2 moles of p-chlorophenylmagnesium chloride-tetrahydrofuran complex under the conditions of Example 6, the resulting productis di (.p-chlorophenyl carbinol.

"EXAMPLE, GQS.,PREPARATION OF 'ETHYL DI (p- CHLOROPHENYL) HYDROX-YACETATE Two moles of p-chlorophenylmagnesium chloride-tetrahydro'furan complex is allowed to react with 1 mole of diethyl oxalate as described in Example 6, and there is obtained ethyl di(p-chlorophenyl)hydroxyacetate.

EXAMPLE 69;-P-REPARATION OF 1,1.4,4-TETRA- DJCHLOROPHEN YL -1,4-DIHYDROXYBUTAN E When 4 moles of p-chlorophenylmagnesium chloridetetrahydrc-furan complex and 1 mole of dibutyl'succinate are caused 10 react according ;to Example 5, the product formed is 1,1,4,4-tetra(p-chlorophenyl)-l,4-dihydroxy- .hutane.

"mWPREPARATION .OF "DItp-CHLORO ZZHHENYL )"METHYL CARBINOL Two moles of p-chlorophenylmagnesium chloride-tetrahydrofuran complex is allowed to react with 1 mole of acetyl chloride under the conditions of Example 5 to yield di(p-chlorophenyl)methylcarbinol.

EXAMPLE 'ZL PREPARATION OF DI(p-CHLORO- RHENXLLRHE YLGARBI OL The xeactiqtl between 2 .mQles of p-chlorophenylmagnesium chloride-tr:trahydrofuran complex and 1 mole of benzoyl chloride by the process of Example 6 gives di(p- 'chloroph'enyl)phenylcarbinol.

EXAMPLE 72.PREPARATION OF ,DI-p-CHLORO- BENZOYL When 2 moles of p-chlorophenylmagnesium chloride- '21 tetrahydrofuran complex and 1 mole of zinc chloride is allowed to react with 1 mole of oxalyl chloride by the process of Example 29, there is obtained di-p-chlorobenzoyl.

EXAMPLE 73.-PREPARATION F p-YCHLORO PHENYL PROPYL KETONE The reaction of equimolar quantities of p-chlorophenylmagnesium chloride-tetrahydrofuran complex and butyronitrile 'under the conditions of Example 6 gives pchlorophenyl propyl ketone.

EXAMPLE 74.-PREPARATION OF o-TOLTJ'ALDEHYDE One mole of o-tolylmagnesium chloride-tetrahydrofuran complex is added to a stirred solution of 4 moles of methyl formate in tetrahydrofuran in the manner described in Example 5. When the organic layer is purified, there is obtained as the final product, o-tolualdehyde, B. P. 194. I

EXAMPLE 75.PREPARATION OF DI(p-'1OLYL)- METHYLCARBINOL The reaction of 2 moles ofp-tolylmagnesium chloridetetrahydrofuran complex and 1 mole of ethyl acetate according to the procedure of Example 6 yields di(ptolyl)methylcarbinol.

EXAMPLE 76. -PREPARATION OF ETHYL DI- (m-TOLYL) HYDROXYACETATE Two moles of m-tolylmagnesium chloride-tetrahydrofuran complex is allowed to react with 1 mole of diethyl oxalate as described in Example 5, and there is obtained ethyl di(m-tolyl) -hydroxyacetate.

EXAMPLE 77.PREPARATION OF METHYL 6,8-DI- -TOLYL)-6-HYDROXYCAPROATE Dimethyl adipate, 1 mole, and p-tolylmagnesium chloride-tetrahydrofuran complex, 2 moles, react together by the procedure of Example 5 to form methyl 6,6-di(pt0lyl)-6-hydroxyacetate.

EXAMPLE 78.PREPARATION OF DI(p-TOLYL) a-FURYLCARBINOL Di(p-tolyl)a-fnrylcarbinol is prepared by allowing 2 moles of p-tolylmagnesium chloride-tetrahydrofuran and 1 mole of methyl furoate to react in the manner described in Example 6.

EXAMPLE 79.--PREPARATION OF DI(p-TOLYL)- PHENYLCARBINOL The reaction between 2 moles of p-tolylmagnesium chloride-tetrahydrofuran complex and 1 mole of benzoyl chloride by the process of Example 5 gives di( tolyl)phenylcarbinol.

EXAMPLE 80.--PREPARATION OF p-TOLYL aFURYL KETONE One mole of p-tolylrnagnesium chloride-tetrahydrofuran complex and 0.5 mole of zinc chloride are allowed to react with one mole of furoyl chloride under the conditions of Example 29. The resulting product is ptoIyla-furyl ketone.

EXAMPLE 8l.-PREPARATION OF ANISALDEHYDE One mole of anisylmagnesium chloride-tetrahydrofuran complex is added to a stirred solution of 4 moles of methyl formate in tetrahydrofuran in the manner described in Example 5. From the organic layer, there is obtained anisaldehyde, B. P. 247 C.

' EXAMPLE 82.-PREPARATION 0F DI(PHENETYL)- v METHYLCARBINOL The reaction of 2 moles of phenetylmagnesium chloride-tetrahydrofiuran complexand 1 mole of ethyl'acetate according to the" process of Example 5 yields di(-phenetyl)methylcarbinol.

EXAMPLE 83.PREPARA'1ION OF BUTYL 4,4 -DIANISYL-4-HYDROXYBUTYRATE I Two moles of anisylmagnesium chloridetetrahydro 22 succinate as described in Example 6, and there is butyl 4,4-dianisyl-4-hydroxybutyrate.

EXAMPLE 84.--PREPARATION 0F 1,1,4-TRI- (PHENETYL)-1,4-DIHYDROXYPENTANE When 3 moles of phenetylmagnesium. chloride-tetrahydrofuran complex react with 1 mole of methyl levulinate according to Example 5, there is obtained 1,1,4- tri(phenetyl)-l,4dihydroxypentane.

EXAMPLE 84a.PREPARATION OF 1,1,4 lRI- (PHENETYL)-1,3-PENTADIENE Dehydration of 1,1,4-tri(phenetyl)-1,4-dihydroxypentane by refluxing it in glacial acetic acid with a crystal of iodine leads to 1,1,4-tri(phenetyl)-1,3-pentadiene.

EXAMPLE 85.PREPARATION OF 5,.ri-DIANISYL- LEVULINIC ACID .Two moles of anisylmagnesium chloride-tetrahydro furan complex reacts with lmole of furoyl chloride under the conditions of Example 5 to give first dianisyl(afuryl)carbinol. When the latter is boiled with dilute hydrochloric acid, ring opening occurs, giving 5,5-dianis'yllevulinic acid.

EXAMPLE 86.--PREPARATION OF DI(3,4-DICHLORO- PHENYMMETHYLCARBINOL When 2 moles of 3,4-dichlorophenylmagnesium chloride-tetrahydrofuran complex is allowed to react with 1 mole of ethyl acetate under the conditions of Example 6, there is obtained di(3,4-dichlorophenyl)methylcarbinol.

EXAMPLE -87.--PREPARATION OF ETHYL DI(3,4-

DICHLOROPHENYL) HYDROXYACETATE Two moles of 3,4-dichlorophenylmagnesium chloridetetrahydrofuran complex react with 1 mole of diethyl oxalate by the procedure of Example 5 to give ethyl di(3,4-dich1orophenyl)hydroxyacetate.

EXAMPLE 88.-PREPARATION OF 1 1,4.4-TETRA- (3,4-DICHLOROPHENYL)-1,4DIHYDRQXYBUTANE When 4 moles of 3,4-dichlorophenylmagnesium chloride-tetrahydrofuran complex and 1 mole of dibutyl succinate react together, the resulting product is 1,1,4,4-tetra (3,4-dichlorophenyl) 1,4-dihydroxybutane.

EXAMPLE 8Sa.PREPARATION 0F 1,1,4,4-TETRA(3,+ DICHLOROPHENYL)-1,3-BUTADIENE Dehydration of 1,l,4,4-tetra(3,4-dichlorophenyl)-l,4e dihydroxybutane by refluxing it in benzene with a trace of p-toluenesulfonic acid gives 1,1,4,4tetra(3,4-dich1orophenyl)-1,3-butadiene.

isolated EXAM LE ill-PREPARATION on ETHYL megs.

TRICHLOROPHENYL)HYDROXYACETATE Two moles of 2,4,S-trichlorophenylmagnesium chloride-tetrahydroturan complex react with 1 mole of diethyl oxalate by the procedure of Example 5 to giveethyl di(2,4,5-trichlorophenyl)hydroxyacetate afa /e375 EXAMPLE '93.-'PREP,ARAT 1 ON OF '1,1,4,4'-TETRA(2,45- TRICHLOROPHENYL)IAJDIHYDROXYBUTANE When 4 moles 'of 2,4,5=trichlorophenylmagnesium chloride-tetrahydrofuran complex and 1 mole of dibutyl succinat-e react together, the resulting product is l,1,4,4- -tetra'(2,4,5-trichlorophenyl)-l,4-clihydroxybutane.

93a.-PREPARATION OF 1,'1,'-l,4-TETRA(2,&,5 TRICHLOROPHENYL) -1,3 BUTA'DIEN E Dehydration of the product of Example 93 by the process of Example 15a yields 1J1,4,4 tetra(2,4,5-tr1chlorophenyl)-1,3-butadiene.

EXAMPLE '94.--'PREPARATION OF 2,4;5 TRICHLOR 'PHENYL METHYL KETONE The reaction of '1 mole of 2 4,S trich'lorophenylmagnesium chloride-tetrahydrofuran complex and 1 mole of acetyl chloride in the presence of zinc chloride as :described in Example 29 "yields '2,4,'5-t1iichlorophenyl methyl ketone.

EXAMPLE 95.'PREPA"RATION OF j2,4,5-TRICHL'OR O- PIIENYL "METHYL 'KETONE 2,4,5-trichlorophenyl methyl ketone is prepared by the reaction of equimolarquantities of 2,4,5-trichlorophenylmagnesium chloride-tetrahydrofuran' complex and acetonitrile under the conditions of Example '5.

EXAMPLE Bil-PREPARATION OF DIp(1,2,4,5-TETRA- CHLOROPHENYL) METHYLCARBINOL When 2 moles of 1,2,4,S-tetrachlorophenylmagnesiurnchloride-tetrahydrofuran complex is allowed to react with 1 'mole "of ethyl acetate under the conditions of Example 6, therejs obtained di( l,2,4,5-tetrachlorophenyl) methylcarbinol.

EXAMPLE 97.PREPARATION OFVETHYL DI(1,2,',5- TETRACHLOROPH'ENYL)'HYDROXYACETATE Two moles of l,2,4,'5tetrachlorophenylmagnesium chloride tetrahyd-rofuran complex 'react with 1 'mole of diethyl *oxalate by ath-e procedure of Example ,5 to give ethyl di( 12;4;5 tetrachlorophenyl)hydroxyacetate.

E M -?PREBARATION OF 1,l,4-. -'TETRA( TETRACHLOROPHENYL) -1,4-DIHYDROXYBUTANE When 4 moles of l,2,4,5-tetrachlorophenylmagnesium chloride-tetrahydrofuran complex and 1 mole of dibutyl succinate .react together, the resulting product is 1,1,41,4- :tetra (l ,2,4,'5-tetrachlorophenyl) 1,4-dihydroxybutane.

EXAMPLE 98a.-PREPARATION QF 1,1,4,4- TETRA(1,2,- 4,5-TETRACHLOROPHENYL)-1,3 BUTADIENE Dehydration of 1;1;4,4tetra( 1,2,4,5-tetrachlo-rophenyl)- 1,4-dihydroxybutane by refluxing it in benzene With a trace r-of p-toluenesulfonic acid 'gives 1,l,4,4-tetra(l,2,4 .5- tetrachlorophenyl)r1,3-butadiene.

EXAMPLE:99.-PREPARATION OF 1,'2, 4,5-TETRA4 CHL'OROPHENYL METHYL KETONE The reaction of 1 mole-of l,2,4,5 tetrachlorophenylmagnesium chloride-tetrahydrofuran complex and 1 mole of acetyl chloride in the presence of zinc chloride as described in "Example 29 yields l,2,4,5-tetrachlorophenyl 'methyl ketone.

EXAMPLE 100.-PREPARATION OF 1,2,4,5-TETRA- CHLOROPHENYL IMETH'YL KETONE l,2,4,5-tetrachlorophenyl methyl ketcne is prepared by the reaction of equimolar quantities of l,2,4,5-tetrachlorophenylmagnesium chloride-tetrahydrofuran complex and :acetonitrile under the'conditions of Example -5.

EXAMPLE 101. .PREP ARATION OF DI (2,3,4,5,6-PENTA- CHLOROPHENYLJ'MEFIYHYL'CARBINOL When '2 moles of 2,3,4,5,6 pentachlorophenylmagne- 'sium chloride-tetrahydrofuran complex is allowed to react with 1 mole of ethyl acetate under the conditions of *Example 6, there is obtained di(2;3,4,5;6 pentachlorophenyUmethylcarbinol.

EXAMPLE 1,02.PREPARATION OF ETHY L 'DI'('2,3;4,'*5,'6- PENTACHLOROPHENYL) HYDROXYACETATE 'Two moles of 2,3,4,5,6-pentachlorophenylmagnesium chloride-tetrahydrofuran complex react with 1 mole of diethyl oxalate by the procedure of Example "5 to give ethyl di(2,3,4,5,6=pentachlorophenyl)hydroxyacetate.

EXAMPLE 1Q3.PREPARATI 0N OF 1,1,4 ,4-TETRA 2,3,4 5,6-PENTACHLOROPHENYL) -I,4QDIHYDROXYBUTANE When 4 moles of 2,3,4,5,6-pentachlorophenylmagnesiurn chloride-tetrahydrofuran complex and 1 mole of dibutyl succinate react together, the resulting product is 1,l,4,4 'tetra(.2,3,4,5,6=- pentachlorophenyl) 1,-4 ---ilihydroxybutane.

EXAMPLE 103a.-PREPARATION OF 1,1,4,:4T ETRA(2;3,4, 'fifi-PENTAGHLOROPHENYL) -1,.3-BUT;AD IENE Dehydration of the product of Example 103 by the process of Example 15a gives 1,l,4,4-tetra(2,.3,4,5,6;pentachlorophenyl) 1,3-butadiene.

EXAMPLE ,104. -PREBARA'.QION OF i-2,.3,4;.5,6-,PENTA- CHLOROPHENYL METHYL KETONE The reaction of 1 mole of 2,3,4,5,6-pentachlorophenylmagnesium chloridetetrahydrofuran complex and 1 mole of acetyl chloride in the presence of zinc chloride as de scribed in Example 29 yields 2,3,4,5,6-pentachlorophenyl methyl ketone.

EXAMPLE 105..PREPARATION OF 2,3,4;5,6PEN'1A- CHLOROPHENYL METHYL KETONE 2,3,4,5,6-pentachlorophenyl methyl ketone is prepared by "the reaction ofequimolar quantities of 2, 3,4;5;l6-pentachlorophenylmagnesium chloride-tetrahydrofuran complex and acetonitrile under the conditions of Example 5.

EXAMPLE Mr-PREPARATION OF 2,6-DIMETHYL- BENZALDEHYDE One mole of Z-m-xylylmagnesiurn chloride-tetrahydrofuran complex is added .to astirred-solution of 4 moles of methyl formate 'in tetrahydrofuran in the manner described in'Example 5. From the organic layer there is isolated 2,6-dimethylbenzaldehyde.

butyl 4,4-di(2-mxylyl) -4-hydroxybutyrate.

EXAMPLE 109..PREP,ARATIQN ,OF 1,1,5t-TRIt2-m- XYLYL) -1,4-DIHYDROXYPEN T AN E Three moles of Z-m-xylylmagnesium chloride-tetrahydrofuran complex react with 1 mole of methyl levulinate by "the process of Example 5. .T he resu'ltingproduct is 1,1,4-tri(2-m-xylyl)-1,4-dihydroxypentane.

EXAMPLE 109a.--PREPARATION OF 1,1,4-TRI('2l-m- XYLYL) -l ,3-PENTADIENE Dehydration of 1,1,4 tri(2-m-xylyl)-1,4-dehy-droxypentane by the process given in Example 15a gives 1,1,4- tri(2-m-xylyl)-1,3-pentadiene.

Two moles of 2-m-xylylma'gnesium *chloride tetrahydrofuran complex react with 1 mole of furoyl chloride under the conditions of Example 5 to give as the first product, di(Z-m-xylyl)a-furylcarbinol. When the latter is g ope in crue EXAMPLE 111.-PREPARAT10N F DI(BIPHENYLYL) METHYLCARBINOL The reaction of 2 moles of hiphenylylmagnesium chloride-tetrahydrofuran complex with 1 mole of ethyl acetate according to the process of Example yields di( biphenylyl)rnethylcarbinol. V

EXAMPLE 112.-PREPARATION OF 1,1-DI(BI- PHENYLYL)-1-DODECANOL When 2 moles of biphenylylmagnesium chloride-tetrahydrofuran complex react with 1 mole of butyl laurate by the method of Example 6, there is obtained 1,1-di(biphenylyl)-1-dodecanol.

EXAMPLE 113.PREPARATION OF ETHYL DI (BIPHENYLYL') HYDROXY ACETATE Ethyl di(biphenylyl)hydroxyacetate is prepared by allowing 2 moles of biphenylylmagnesium chloride-tetrahydro furan complex to react with 1 mole of diethyl oxalate under the conditions of Example 5.

EXAMPLE 114.PREPARATION OF ETHYL 10,10-DI- (BIPHENYLYL)--HYDROXYCAPRATE The reaction of 2 moles of biphenylylmagnesium .chloride-tetrahydrofuran complex with 1 mole of diethyl sebacate according to Example 5 yields ethyl 10,l0-di(b iphenylyl -l 0-hydroxyc aprate.

EXAMPLE 114a.-PREPARATION OF ETHYL 10,10-DI- (BIPHENYLYm-Q-DECEEOATE v The product of Example 114 is dehydrated in the manner described in Example 12a to give ethyl l0,10-di(bi phenylyl)-9-decenoate. I I

EXAMPLE 115.-PREPARA'rr0N OF METHYL 4 er- PHENYLYL-4-HYDROXYVALERATE Equimolar quantities of biphenylylmagnesium chloride-tetrahydrofuran complex and methyl levulinate are are allowed to react together by the process of Example 6, and the resulting product is methyl 4-trichlorobiphen ylyl-4-hydroxyvalerate.

EXAMPLE 118a.-PREPARATION OF METHYL 4-TRI- CHLOROBIPHENYLYL-Ei-PENTENOATE Dehydration of the product from Example l18 by the procedure of Example a gives methyl 4-trichlorobiphenylyl-3-pentenoate. 1

EXAMPLE 119.--PREPARATION 0F METHYL 4-NONA- CHLOROBIPHENYLYL-A-HYDROXYVALERATE Equimolar quantities of nonachlorobiphenylylmagnesium chloride-tetrahydrofuran complex and methyl levulinate are allowed to react by the procedure of Example 5 to yield methyl 4-nonachlorobiphenylyll-hydroxyvalerate.

EXAMPLE 120.PREPARATION OF NAPETEAL DEHYDE V One mole of naphthylmagnesium chloride-tetrahydrm furan complex is added to a stirred solution of 4 moles of methyl formate in tetrahydrofuran in; the mannerrde- Equimolar scribed in Example 4. 'From the organiclayer, there is isolated naphthaldehyde.

EXAMPLE l21.--PREPARATION OF DINAPHTHYL- METHYLCARBINOL EXAMPLE 1'23.PREPARATION OF ETHYL DI(CHLORO- N APHTHYL) HYDROXYACETATE When 2 moles of chloronaphthylmagnesium chloridetetrahydrofuran complex react with 1 mole ofdiethyl oxalate, under the conditions of Example 5, the final product is ethyl di(chloronaphthyl)hydroxyacetate. EXAMPLE 124.PREPARATION OF CHLORONAPHTHYL METHYL KETONE quantities of chloronaphthylmagnesium chloride-tetrahydrofuran complex and acetyl chloride in the presence of zinc chloride react together in the manner described in Example 29 to give chloronaphthyl methyl ketone. I

EXAMPLE 125.PREPARATION 0F DI-(TRIFLUORO- METHYLPHENYL) METHYLCARBINOL The reaction of 2 moles of trifiuoromethylphenylmagnesium chloride-tetrahydrofuran complex and 1 mole of ethyl acetate according to the procedure of Example 5 yields di(trifluoromethylphenyl)methylcarbinol. EXAMPLE a.--PREPARATION 0F a,a-DI(TRIFLUORO- METHYLPHENYL ETHYLENE The product from Example 125 is dehydrated under the conditions of Example 12a, giving a,ot-di(trifiuoro methylphenyl) ethylene.

EXAMPLE 126.PREPARA1ION OF ETHYL DI(TRI-.

FLUOROMETHYLPHENYL)HYDROXYACETATE When 2 moles of trifluoromethylphenylmagnesium -chloride-tetrahydrofuran complex react with 1 mole of diethyl oxalate under the conditions of Example 6, there is obtained ethyl di(trifiuoromethylphenyl)hydroxy acetate.

EXAMPLE 127.PREPARATION OF BU'TYL 4,4DI(TRI- FLUOROMETHYLPHENYL) -4-HYDROXYBUTRATE Two moles of trifluoromethylphenylmagnesium chlm '-ride-tetrahydrofuran complex react with 1 mole of dibutyl succinate by the process of Example '5 to yield butyl 4,4-di(trifluoromethylphenyl)-4-hydroxybutyrate.

EXAMPLE 128.--PREPARATION OF 1,1,B,6-TETRA(TRI- FLUOROMETHYLPHENYL -1 ,G-DIHYDROXYHEXANE The reaction between 4 moles of trifiuorornethylphenyl- .magnesium chloride-tetrahydrofuran complex andtl mole of dimethyl adipate by the procedure of Example 6 leads to 1,1,6,6 tetra(trifluoromethylphenyl) 1,6 dihydroxyhexane.

EXAMPLE 129.PREPARATION OF DI(TRIFLUORO- METHYLPHENYL) PHENYLCARBINOL When 2 moles of trifiuoromethylphenylmagnesium .chloride tetrahydrofuran complex are allowed to react EXAMPLE .PREPARATION OF 5,5-DI(TRIFLUORO- METHYLPHENYL)LEVULINIC CID M Two moles of trifluoromethylphenylmagnesiurn. ch10.-

ride-tetrahydrofur'an complex react with 1 mole of methyl f y I furoate under the conditions of Example to give as the first product, di(trifluoromethylphenyl)a-furylcarbinol. When the latter is boiled with dilute hydrochloric acid, ring opening occurs, giving 5,5-di(trifluoromethyltion of 4 moles of methyl formate in tetrahydrofuran in tthe manner described in Example 5. When :the organic .-layer is purified, there is obtained palimethylamino- "benzaldehyde, M. P. 74 C.

EXAMPLE 134.PREPARATION OF DI(p-DIETHYL- AMINOPHENYL) CARBINOL When 1 mole of methyl formate is added to two moles of p-diethylaminophenylmagnesium chloride-tetrahydro- 'furan complex under the conditions of Example 6, the resulting product is di(p-diethylaminophenyl)carbinol.

EXAMPLE l35.-PREPARATION OF DI(p DIMETI-IYL- AMINOPHENYLHYIETHYL CARBINOL The reaction between 2 moles of p-dimethylamino- :phenylmagnesium chloride-tetrahydrofuran complex and 1 mole of ethyl acetate by the process of Example 5 gives di(p-dimethyl'arninophenyl)methylcarbinol. EXAMPLE 1'36.PREPARATION OF 1,l-DI(p-DI1\1ETHYL- AMINOPHENYL) -1DODECANOL When 2 moles of '-p-dimethylaminophenylmagnesium -'chloride-tetrahydrofuran complex react with 1 mole of 'butyl 'laurate by the method of Example 6, there is ob- ;tained 1,'-1-di (p-dimethylaminophenyl)-1-dodecanol.

EXAMPLE 137.PREPARATION OF 1,1-DI (p-DIMETHYL- AMINOPHENYL)OCTADECEN-Q-OL-l Two moles of p-dimethylaminophenylmagnesium chlo- -ride-tetrahydrofu-ran complex react with 1 mole of methyl oleate under the conditions of 'Example 6 toyield 1,1zdi(p-dimethylaminophenyl)octadecen-9-ol1.

EXAMPLE 138.-PREPARATION OF ETHYL DI(-p-DI- .EIHYL'AMINOPHENYL)iHYDRfOXYACETATE The reaction of 2 moles ofp-diethylaminophenylmag- -nesium chloride-tetrahydrofuran complex'with il mole of diethyl oxalate according to the method of Example '5 ,rg-ivesasthe final product ethyl di(p-diethylaminophenyl) 'hydroxyacetate.

EXAMPLE 139.PREPARATION OF 1,1,2,2-TETRA(p-DI- "ME THYLAM'INOPHENYL ETHYIl/ENE GLYCOL When 4 moles of -p-dimethylaminophenylmagnesium .chloride tetrahydrofuran complex are allowed to react with .lmole of-diethyl oxalate in-themanner described in Example :6, the product obtained is -l;=l;2;2, tetra'(p-dirmethylaminophenyl)ethylene glycol.

EXAMPLE 140.-PREPARATION OF 1,1,4,4-'TETRA(p-D'I-- JMELRHXLA'MINOPHENYL .-.1,4:DIHYDRQXJY BLUTAINE 4 The reaction of 4 moles of p-dimethylaminophenylmagnesium v chloride-tetrahydrofuran complex and 1 "mole :qfladibutyl -=succ inate ibyzthe method of Example :5 leads m l,l,4,4-tetra(p dimethylanrinophenyl)- ,4- y I Y- butane.

.EXAMPLE ML-TPREPARACELQN OF V1,1,e,6 f1 ETRA ,DI-

ZMES IHYLAMINOPHENYL)-1,6-DIHYDR0XYHEXANE Four moles of p-dimethylaminophenylmagnesiurn chloride-tetrahydrofuran complex react with 1 mole of dimethyl adipate under the conditions of Example 6 to give l,l,6,6-tetr a( p dimethylaminophenyl) 1,6 dihydroxyhexane.

EXAMPLE Mae-PREPARATION LOF p-PHENYLENE BIS (DI(p-DIMETHYLAMINOPHENYL)CARBINOL) p-Phenylene bis ,(ditp:dimethylaminophenfl)carbinol) is prepared by the reaction of 4 moles of p-dimethylaminophenylmagnesium chloride-tetrahydrofuran complex with '1 mole of diethyl terephthalate, using the process ofExample 5.

EXAMPLE 145.PREPARATION 0F DIOJ-DIMETIIYL AMINOPHENYL)ANISYLCARBINOL Two moles of p-dimethylaminophenylmagnesium chloride-tetrahydrofuran complex are allowed to react with 1 mole of methyl anisate by the method of Example 6.

From the organic layer, there is obtained di(p-dimethyl aminophenyl)anisylcarbinol.

EXAMPLE 146.-PREPA,RATION 0F DI (p-DIETHYL- AMINOPHENYL)a-FURYLCARBINOL When 2 moles of p-diethylaminophenylmagnesium chloride-tetrahydrofuran complex are caused to react with 1 mole of methyl furoate under the conditions of Example 6, the resulting product is di(p-diethylaminophenyl)afurylcarbinol.

EXAMPLE 147.-.-PREPARATION OF DI(p-DIMETHYL- AMINOPHENYL) (2,4 -DICHLOROPHENOXYMETHYM- CA'RBINOL The reaction between 2 moles of p'dimethylamino phenylmagnesium chloride-tetrahydrofuran complex and 1 mole of 'butyl 2,4-dichlorophenoxyacetate by the meth- 0d of Example 5 gives di'(p-dimethylaminophenyl)(2,4-

dichlorophenoxymethyl)-carbinol.

EXAMPLE 148.PREPA;RATION 0F 1,1,4' TRI(pDIHETH- YLAMINOPHENYLY)-1,4-DIHYDROXYPENTANE Three moles of p-dimethylaminophenylmagnesium chloride-tetrahydrofuran complex react by the procedure of Example 6 with '1 mole of methyl levulinate to give 1,1,4-tri(p-dimethylaminophenyD-1,4-dihydroxypentaue.

EXAMPLE 149.-PREPARATION on nlt mMmlnyL- AMINQPHENYL)METHYLCARBINQL The action f 2 moles of p-dimethyl minophenylmagnesium chloride-tetrahydrqfuran complex with :1 mole of acetyl chloride by the method described in Example 5 yields di(p-d imethylaminophenyl)methylcarbinol.

EXAMPLE I50. PREB RA1IION 10F .DI-METHYLAMENO- PHENYL METHYL KETONE When 1 mole of p-dimethylaminophenylmagnesium chlorid etra ydrofuran comp x, .5 mole ofzincchloride, and 1 mole of acetylchloride aretallowed to react according to .thepr ce ure of Ex mple .29, thereis obtained dirnethylaminophenyl methyl ketone.

EXAMPLE 151.PREPA'RATION OF DIMETHY-LAMINO- PHENYL PHEN-YL KETDNE Equimolar quantities of p-dimethylaminophenylmagnesium-chloride-tetrahy of ran complex and benzoyl chl ri e (in he p e enc of zinc chloride) rea in the m nneridescrihedin Example 2.9 to yield ime hylamino r2l1enx1 pl;1eny1 ketone. V

EXAMPLE 152.-PREPARATION 0F DI(p-'DII\I-ETH'YL- AMI'NOBENZOXL) 7 Two moles of p-dimethylaminophenylmagnesium chlo- -ride:tetrahydrofuran complex react :with 1 mole of-oxalyl -chloride (zinc :chloride :present) under the conditions of Example I29 to give .di(p:dim ethylaminobenzoyl) phenylcarbinol.

garages EXAMPLE 153.PREPARATIN 0F ETHYL B-(p-DI- METHYLAMINOBENZOYL PROPIONATE Equimola'r quantities of p-dimethylaminophenylmagnesium chloride and the acid chloride of monoethyl succinate are allowed to react in the manner described in Example 29 (zincchloride present) to yield ethyl (3-(pdimethylaminobenzoyl) propionate. EXAMPLE 154.-PR1 1PARATION OF 1,1,6,6TETRA(p-DI- METHYLAMINOPHENYL)-1,G-DIHYDROXYHEXANE ,Four moles of p-dimethylaminophenylmagnesium chloride are allowed to react with 1 mole of adipoyl dichloride under the conditions of Example 5, giving as the final product, 1,1,6,6-tetra(p-dimethylaminophenyl)-1,6-

dihydroxyhexane.

vEXAMPLE l54a.-PREPARATION OF 1,1,6,6-TETRA(p- DIMETHYLAMINOPHENYL)-1,5-HEXADIENE The dehydration of the product from Example 154 by -the procedure of Example 15a gives 1,1,6,6-tetra(p-dimethylaminophenyl)-1,5-hexadine. EXAMPLE l55.-PREPARATION OF p-DIMETHYLAMINO- PHENYL METHYL KETONE Equimolar quantities of p-dimethylaminophenylmagnesium chloride-tetrahydrofuran complex and acetonitrile are allowed to react by the method of Example 6. The

resulting product is p-dimethylaminophenyl methyl ketone.

EXAMPLE l56.-PREPARATION OF p-DIETHYLAMINO- PHENYL PHENYL KETONE Equimolar quantities of p-diethylaminophenylmagnesium chloride-tetrahydrofuran complex and benzonitrile react by the procedure of Example to yield p-diethylaminophenyl phenyl ketone. EXAMPLE 157 PREPARATION OF DI(CHLOROTOLYL)- METHYLCARBINOL Two moles of chlorotolylmagnesium chloride-tetrahyidrofuran complex react with 1 mole of ethyl acetate under the conditions of Example 5 to give di(chl'orotolyl)- methylcarbinol. EXAMPLE 158.PREPARATION 0F ETHYL DI(CHLORO- TOLYL)HYDROXYACETATE When 2 moles of chlorotolylmagnesium chloride-tetrahydrofuran complex react with 1 mole of diethyl oxalate by the process of Example 6, there is obtained ethyl di- (chlorotolyl)hydroxyacetate.

.. 1,1,6,6-tetra(chlorotolyl)-1,6-dihydroxyhexane.

EXAMPLE ISL-PREPARATION 0F ETHYL 3,4,4-TRI- (CHLOROTOLYL)-4HYDROXYBUTYRATE Three moles of chlorotolylmagnesium chloride-tetrahydrofuran complex. add to 1 mole of diethyl mal eate under the conditions of Example 5 to give ethyl 3,4,4- tri (chlorotolyl) -4-hydroxybutyrate.

EXAMPLE 162.-PREPARATION OF DI(CHLOROTOLYL)- PHENYLCARBINOL The conditions of Example 6 are followed, using 2 moles of chlorotolylmagnesium chloride-tetrahydrofuran complex andl mole of methyl benzoate as reactants, and

the product isolated from the filtrate is di(chlorotolyl)- EXAMPLE 163.-PREPARATION 0F DI(CHLOROTOLYL)- u-FURYLCARBINOL The reaction between 2 moles of chlorotolylmagnesium chloride-tetrahydrofuran complex and 1 mole of methyl furoate according to the procedure of Example 5 gives di(chlorotolyl) u-furylcarbinol.

EXAMPLE 163a.PREPARATION OF 5,5-DI(CHLO'RO' TOLYL)LEVULINIC ACID When di(chlorotolyl)a-furylcarbinol is boiled with dilute hydrochloric acid, ring opening occurs to yield 5,5-di(chlorotolyl)levulinic acid.

EXAMPLE 164.-.PREPARATION OF CHLOR'OTOLYL METHYL KETONE Equirnolar. quantities of chlorotolylmagne'sium chloride-tetrahydrofuran complex and acetyl chloride reactin the presence of zinc chloride in the manner described in Example '29 to give chlorotolyl methyl ltetone.

EXAMPLE 165.PREPARATION OF B'IStCHLORO- TOLUYL) When 2 moles of chlorotolylmagnesium chloride-tetrahydrofuran complex are allowed to react with -1 mole of oxalyl chloride (1 mole of zinc chloride present) by the process of Example 29 there is obtained bis(chlorotoluyl).

EXAMPLE 166.PREPARATION OF CHLOROTOLYL PHENYL KE'IONE Equimolar quantities of chlorotolylmagnesium chloride-tetrahydrofuran complex and benzonitrile are allowed to react under the conditions of Example 5 to give chlorotolyl phenyl ketone.

EXAMPLE 167.PREPARATION OF DI(CHLOR0- ANISYL)METHYLCARBINOL Two moles of chloroanisylmagnesium chloride-tetrahydrofuran complex react with 1 mole of ethyl acetate under the conditions of Example 5 to give di(chloro anisyl)methylcarbinol.

EXAMPLE 168.-PREPARATION OF ETHYL DI(CHLORO- ANISYL)HYDROXYACETATE When 2 moles of chloroanisylmagnesium chloridetetrahydrofuran complex react with 1 mole of diethyl oxalate by the process of Example 6, there is obtained ethyl di(chloroanisyl)hydroxyacetate.

EXAMPLE 169.PREPARATION OF METHYL 6,6-DI- CHLOROANISYL)-6-HYDROXYCAPROATE The reaction between 2 moles of chloroanisylmagnesium chloride-tetrahydrofuran complex and 1 mole of dimethyl adipate by the procedure of Example 6 gives as the final product, methyl 6,6-di(chloroanisyl)-6-hydroxycaproate.

EXAMPLE 170.PREPARATION 0F 1,1,6,6-TETRA- (CHLOROANISYL)-1,6-DIHYDROXIYHEXANE Four moles of chloroanisylmagnesium chloride-tetrahydrofuran complex and 1 mole of dimethyl adipate are allowed to react together in the manner described in Example 5. From the organic layer there is isolated 1,1,6,6-tetra(chloroanisyl) -l,6-dihydroxyhcxane.

EXAMPLE 171.PREPARATION 0F ETHYL 3,4,4-TR'I- (CHLOROANISYL)-4-HYDROXYBUTYRATE Three moles of chloroanisylmagnesium chloride-tetrahydrofuran complex add to 1 mole of diethyl maleate under the conditions of Example 5 to give ethyl 3,4,4-

tri (chloroanisyl -4-hydroxybutyrate.

EXAMPLE 172. PREPARATIoN OF DI(CHLOR0- ANISYLIPHENYLCARBIN'OL The conditions of Example 6 are followed, using 2 moles of chloroanisylmagnesium chloride-tetrahydrofuran complex and 1 mole of methyl be'nzoate as reactants,

and the product isolated from the filtrate is di(chlor0- anisyUphenylcarbiriol.

EXAMPLE 175.--PREPA'RATION on BIS(CHLOR ANISOYL) When 2 moles of tchloroanisylmagnesium chloridetetrahydrofuran complex are allowed to react with 1 mole of oxalyl chloride (1 mole of Zinc chloride present) by the process of Example 29 there is obtained bis(chloroanisoyl).

vEXAIVIPLE 176.-PREPA RA'ITON OF CHLOROANISYL iPHENYL KETONE Equimolar quantities of chloroanisylmagnesium chloride-tetrahydrofuran complex and benzonitrile are allowed to react under the conditions .of Example to give chloroanisyl phenyl ketone.

EXAMPLE 17 7 .'PREPA1RATION OF DI"(CHLORO- PHENETYL) METHYLCARB IN-OL Twomoles of chlorophenetylmagnesium chloride-tetra- ,hydrofuran complex react with '1 mole of ethyl acetate under the conditions of Example 5 to give di(chlorophenetyl methylcarbinol.

EXAMPLE 178.PREPARATION 0F nrnrri DI(CHLO RO PHENETYL') HYDROXYACETATE When 2 moles of chlorophenetylmagnesium chloridetetrahydrofuran complex react with 1 mole of diethyl oxalate by the process of Example 6, there is obtained ethyl di(chlorophenetyl) hydroxyacetate.

EXAMPLE 179.PREPARATI'ON 0F METHYL (id-DI- (CHLO'ROPHENETYL)-6 HYDROXYCAPROATE The reaction between '2 moles of chlorophenetylmag nesium chloride-tetra'hydrofuran complex and 1 mole of dimethyl adipate by the procedure of Example 6 gives as the final product, methyl 6,6-di(chlorophenetyl)-6- hydroxycaproate.

EXAMPLE 180.-PREPARATION 0F 1,1,6,6-TETRA- (CHLOROPHENETYL)-1,6-DIHYDROXYHEXANE Four moles of chlorophenetylmagnesium chloride- =tetrahydr0furan complex and l-mole of dimethyl adipate are allowed to react together in the manner described in vliJt ullilJle 52. From the organic layer there is isolated 1,1,6,6-tetra(chlorophenetyl)-1,6hydroxyhexane.

EXAMPLE 1,8l.-I-REPARATION OF ETHYL 3,4,l-TR-I- (CHLOROPHENETYL)4-HYDROXYBUTYRATE Three moles of chlorophenetylmagnesium chloridetetrahydrofuran' complex add to 1 mole of diethyl maleate under the conditions of Example 5 to give ethyl 3,4,4-tr1(chlorophenetyl) =4-hydroxybutyrate.

IEXAMILE 182,-'PREPA'RA'IION OF DI(CHL'ORO- PHENETYL')PHENYLCARBINOL The conditions of Example 6 are followed, using ,2 moles of chlorophenetylmagnes'ium chloride-tetrahyclrofuran complex and '1 mole of methyl'benzoate as reactants,

and the product isolated from the filtrate is di'(clhlorov phenetyl)phenylcarbino1.

EXAMPLE ,183.PREPARATION OF DI(CHLORO- PHENETYL)a-FURYLCARBINOL 'The reaction between 2 moles of chlorophenetylmagnesium chloride-tetrahydrofuran complex and 1 mole-of methyl .furoate according to the procedure of Example 5 gives di(chlorophenetyl) a-furylcarbinoL EXAMPLE 183a.PREPARATION 0F 5,5-DI(CHLORO- PHENETYL)LEVULINIC ACID When di(chlorophenetyl) av-furylcarbinolis boiled with dilute hydrochloric acid, ring opening occurs to yield 5 ,5-di(chlorophenetyl)levulinic acid.

EXAMPLE l84;1PREPARATIONOF CHLOROPHENETY L METHYL KETONE Equimolar quantities of chlorophenetylmagnesium chloride-tetrahydrofuran complex and acetyl chloride .react in the presence of zinc chloride in the manner described in Example 29 to ,give chlorophenetyl methyl ketone.

EXAMPLE 185.PREPARATION 0F BIS(CHLOR0-p- ETHOXYBENZOYL) When 2 moles of chlorophenetylmagnesium chloridetetrahydrofuran complex are allowed to react with 1 mole-of oxalyl chloride 1 mole of zinc chloride present) by the process of Example 29 there is obtained bis(chloro-p-ethoxy-benzoyl).

EXAMPLE 186.PREPARATION on CHLOROPHENETYL PHENYL KETONE Equimolar quantities of chlorophenetylmagnesium chloride-tetrahydrofuran complex and benzonitrile are allowed to react under the conditions of Example 5 to give chlorophenetyl phenyl ketone.

EXAMPLE 187.P,REPABATION OF DI (ETI-IYLTETRi-L CHL OROPHENYL) -METHYLCARBINOL The reaction of 2 moles ofrethyltetrachlorophenylmagnesium chloride-tetrahydrofuran complex with 1 mole \of ethyl acetate according to the method of Example 5 gives di(ethyltetrachlorophenyl)methylcarbinol.

EXAMPLE 188.PREPARATION OF 2-THIOPHENE- ALDEHYDE One mole of Z-thienylmagnesium chloride-tetrahydrofuran complex is added to a stirred solution of 4 moles of methyl formate in tetrahydrofuran in the manner described in Example 4. From the organic layer there is obtained 2-thiophenealdehyde.

EXAMPLE 189.-PREPARATION 0F DI(2-THIENYL;)-

CARBINOL When 1 mole of methyl formate is added to .2 moles of Z-thienylmagnesium chloride-tetrahydrofuran complex under the conditions of Example 6, the resulting product is di(2- thieny1)carbino1.

EXAMPLE 190. -PREPARATION 0F DI(2-THIENL)- METHYLCARBINOL Two moles of Z-thienylmagnesium chloride-tetrahydro- :furan, complex are allowed to react with '1 mole of ethyl acetate using the procedure of Example 5. The product thus obtained is di(2-thienyl)methylcarbinol.

EXAMPLE 19L-PREPARATION OF ETHYL DI(2- "lI-IIENYL)HYD-ROXYACETATE The reaction between 2 moles of 2-thienylmagnesiur'n ehloride-tetrahydrofuran complex and 1 mole of diethyl oxalate by the method of Example 6 yields ethyl di (Z-thienyl hydroxyacetate.

EXAMPLE 192.P REP,A;RATION or 1,1,10,10-TETRA(2- THIENYL)-1,10-DIHYDROXYDECANE When 4 moles of Z-thienylmagnesium chloride-tetra hydrqfuran complex are allowed to react with 1 mole Qf diethyl ,sebacate under the conditions of Example 5, there is obtained 1,1,10,l0-tetra(2-thienyl)-1,l0-dihydroxydecane.

-- EXAM LEioa rrnmPAaAirroN oEs AmRn TllIENYL)4-4HYDROXYBUTYRATE Three moles of 2-thienylmagnesium chloride-tetrahydrofurancomplexadd to 1 mole of diethyl maleate underthe conditions of Example 5 to give 3,4,4-tri(2- thienyl) -4-hydroxybutyrate.

EXAMPLE 194.-PREPARA'r10N F DI(2-THIENYL)- PHENYLCARBINOL EXAMPLE 196.-PREPARATION OF DI (2-THIENYL)- (3-PYRIDYL) CARBINOL A ',Two moles of 2-thienylmagnesium chloride-tetrahydrofuran complex react with 1 mole of methyl nicotinate under the conditions of Example 6 to yield di(2-thienyl) (3-pyridyl)carbinol. a

EXAMPLE 197.-PREPARATION or METHYL 4-(2- TI-IIENYL) l-EHYDROXYVALERATE Equimolar quantities of Z-thienylmagnesium chloridetetrahydrofuran ,complex and methyl levulinate are allowed to react by the procedure of Example 5 to give methyl 4-(2-thienyl)-4-hydroxyvalerate.

, EXAMPLE 198.-PREPARATION O13 2-THIENYL METHYL KETONE The reaction between 1 mole of 2-thieny1magnesium chloride tetrahydrofuran complex, 0.5 mole of zinc chloride,-and 1 mole of acetyl chloride by the process of Example 29 gives as the final product 2-thienyl methyl ketone.

EXAMPLE 199.-PREPARATION 0F 2-THIENYL PHENYL I, V XETONE The conditions of Example 29 are followed, using equimolar quantities of Z-thienyImagnesium chloridetetrahydrofuran complex and benzoyl chloride as reactants in the presence of zinc chloride. The resulting product is Z-thienyl phenyl ketone.

EXAMPLE 200. PREPAR ATION OF DI(2-THENOY L) Two moles of Z-thienylmagnesium chloride-tetrahydrofuran complex react with 1 mole of oxalyl chloride (zinc chloride present) under the conditions of Example 29 to yield di-(Z-thenoyl).

EXAMPLE ZOL- -PREPARATION OF ETHYL ,8(2'-' THENOYL)PROPIONATE When 'equimolar quantities of Z-thienyImagnesium chloride-tetrahydrofuran complex and the acid chloride of'monoethyl succinate are allowed to react according to Example 29 (zinc chloride present), there is obtained ethyl fl-(Z-thenoyDpropionate. A

EXAMPLE 202.--PREPARATION OF 2-1HIENYL a-FURYL KEIONE The reaction between 1 mole of Z-thienylmagnesium chloride-tetrahydrofuran complex, 0.5 mole of zinc chloride, and -1 mole of furoyl chloride in the manner described in Example 29 leads to Z-thienyl u-furyl ketone.

EXAMPLE 2OHJ-Q-PREPAEATION OF Z-THIENYL METHYL KETONE nEquimolari quantities of Z-thienyImagnesium chloridetetrahydrofuran complex and acetonitrile are allowed to react by the procedure of Example 5. The product thus obtained is Z-thienyl methyl ketone. 2

obtained di(2-thienyl) A .5 34... EXAMPL 2O4.--PEEPAR TI N OF Z 'IHIENYL PHENYL KETONE One mole of Z-thienylmagnesium chloride-tetrahydrm furan complex reacts withl mole of benzonitrile under the conditions of Example 6 to yield Z-thienyl phenyl ketone. a

EXAMPLE ZOE-PREPARATION OF PYRIDINE-Sl- I ALDEHYDE One mole of 2-pyridylmagne's lum chloride-tetrahydro furan complex is added to a stirred solution of 4 moles of methyl formate in tetrahydrofu'ran in the manner described in Example 4. From the organic layer there is obtained pyridine-Z-aldehyde; r

EXAMPLE 206.-PREPARATION 0F DItQ-PYRIDYL) CARBINOI; V

When 1 mole of methyl form'ate is added to 2 moles of Z-pyridylmagnesiurn chloride-tetrahyclrofuran complex under the conditions of Example 6,'the resulting product is di(2-pyridyl) carbinol.

EXAMPLE 207-.-PREPARATION 0F IDI(2-PY RIDYL)- METHYLCARBINOL I Two moles of Z-pyridylmagnesium chloride-tetrahydrofuran complex are allowed to react with 1 mole of ethyl acetate using the procedure of Example 5. -The-product thus obtained is di(2-pyridyl)methylcarbinol. v

EXAMPLE 20s.-PREPARAT10N OF ETHYL D102 PYEIDYL)HYDROXYACETATE The reaction between '2 moles of 2-pyridylmagnesiun1 chloride-tetrahydrofuran complex and 1 :mole of diethyl oxalate by the method of Example-6 yields ethyl di(2- pyridyl) -hydroxyacetate.

EXAMPLE 209.-PREPA-RATIoN OF 1,1,10,10-TETRA(2- PYRIDYL) -l,lOeDIHYDROXYDECANE When 4 moles of Z-pyridylmagnesium chloride-tetrahydrofuran complex are allowed to'react with 1 mole of diethyl sebacate under the conditions of Example 5, there is obtained 1,1,10,l0-tetra(2-pyridyl)-l,10-dihydroxy decane. a

EXAMPLE Mir-PREPARATION or DI(2-PYRIDY L)- PHEN C BINOL l T he reaction between 2 moles of 2-pyridylmagnesium chloride-tetrahydrofuran complex and 1 mole of methyl benzoate is carried out in the manner described in Example 6. From the organic layer there is isolated di(2- pyridyl)phenyl carbinol.

EXAMPLE 212.-PREPARATION 0F DI(2-PYRIDYL)o- FUEYLCARBINOL When 2' moles of 2-pyr idylmagnesium chloride-tetrahydrofuran 'com'plexare caused-to react with lmole of methyl furoate by the procedure of Example 5, there is: obtained di(2-pyridyl)a-furylcarbinol. V

EXAMPLE 213.-PREPARATION OF DI(2-PYRIDYL) (3- PYRIDS ZL) CARBINOL Two moles of Z-pyridylmagnesium chloride-tetrahydrofuran complex react with 1 mole of methyl nicotinate under the'conditions of Example 6 .to yield di(2-pyridyl) (3-pyridyl)-carbinol.

EXAMPLE 214. -P BEPARATION OF METHYL 4-(2 PY'RIDYL) LHYDROXYVALERATE Equimolar quantities of 2-pyridylmagnesium chloride- 35 EXAMPLE 215. PREPARATION F 2-PYRIDYL METHYL KETONE The reaction between 1 mole of Z-pyridyImagnesium chloride tetrahydrofuran complex, 0.5 mole of zinc chloride, and 1 mole of acetyl chloride by the process of Example 29 gives as the final product Z-pyridyl methyl ketone.

EXAMPLE 21c. -1 REPARATION OF 2 PYRIDYL PHENYL KETONE The conditions of Example 29 are followed, using equimolar quantities of Z-pyridylma'gnesium chloride-tetrahydrofuran complex and benzoyl chloride as reactants in the presence of zinc chloride. The resulting product is Z-pyridyl phenyl ketone.

EXAMPLE 217.PREPARATION OF DIPICOLINOYL Two moles of Z-pyrid'ylmagnesium chloride-tetrahydrd furan complex react with 1 mole of oxalyl chloride (zinc chloride present) under the conditions of Example 29 to yield dipicolinoyl.

"EXAMPLE fis -PREPARATION OE-ETHYL B-PICOLINOYLPROPIONATE When eqnimolar quantities of Z-pyridyhriagnesium chloride-tetrahydrofuran complex and the acid chloride of monoethyl 'succinate are allowed to react according to Example 29 (zinc chloride present), there is obtained ethyl fi-picolinoyl-propionate.

EXAMPLE 219.4-PREPARATION 0B Z-PYRIDYL a-FURYL KETONE The reaction between 1 mole of 2-pyridylmagnesium chloride-tetrahydrofuran complex, 0.5 mole of zinc chloride, and 1 mole of furoyl chloride in the manner described in Example 29 leads to Z-pyridyI-a-furyl ketone.

EXAMPLE 220.PREPARATION 0F 2-PYRIDYL METHYL KETONE Equimolar quantities of 2-pyridylmagnesium chloridetetrahydrofuran complex and acetonitrile are allowed to react by the procedure of Example 5. The product thus obtained is 2-pyridyl methyl ketone.

EXAMPLE 221.PREPARATION OF 2 PYRIDYL PHENYL KETONE One mole of Z-pyridylmagnesium chloride tetrahydrofuran complex reacts with 1 mole of benzonitrile under the conditions of Example 6 to yield 2-pyridy1 phenyl ketone.

EXAMPLE 222.-PREPARATION OF FURFU'RAL One mole of a-furylmagnesium chloride-tetrahydrofuran complex is added to'a stirredsolution of 4 moles of methyl formate in tetrahydrofuran in the manner described in Example '4. From the organic layer there'is obtained furfural; l

EXAMPLE 223. PREPARATION 0E DI(cr-FURYL)- CARBINOL When 1 mole of methyl formate is added to 2 moles of wfurylmagnesium chloride tetrahydrofuran complex under the conditions ofExample 6, the resulting product is di(a-furyl) carbinol.

EXAMPLE 224.-P REPARATION OF DI ((Y-FURYL)- METHYLGARBINOL Two moles of oc-furylmagnesium chloride-tetrahydrofuran complex are allowed to react with 1 mole of ethyl acetate, using the procedure of Example 5. The product thus obtained is di(a-furyl)methylcarbinol.

EXAMPLE 225.PREPARATION OF ETHYLDIQ- FURYL) HYDROXYACETATE The reaction between 2 moles of a-furylmagn'esium chloride-tetrahydrofuran complex and l-mole of diethyl oxalate by the method of Example 6 yields ethyl di(ofuryDhydroxyacetate. V

-chloride-tetrahydrofuran complex and 1 mole of methyl benzoate is carried out in the manner described inExample 6. From the organic layer there is isolated 'di(or furyl) phenyl-carbinol.

EXAMPLE 229.-P-REPARATION v0F TRIWEURYL CARBINOL When 2 moles of 'a-furylmagnesium chloride tetrahy drofuran complex are caused to react with 1 mole of methyl furoate by the procedure of Example 5, there is obtained tri(a-furyl)-carbinol.

EXAMPLE 230.--PREPARATION 0E DI(a'-FURYL)- (3-PYRIDYL) CA'RBINOL Two moles of ot-furylmagnesium chloridetetrahydrofuran complex react with 1 mole of'methyl nicotinatc under the conditions of Example 6 to yield di( a-furyl) ('3- pyridyD-carbinol.

EXAMPLE 231.PREPARATION OF METHYL Ma FURYL)-4-HYDROXYVALERATE Equimolar quantities of a-furylmagnesium chloridetetrahydrofuran complex and methyl levulinate are "allowed to react by the procedure of Example 5 'togive methyl 4-( a-furyl)-4-hydroxyvalerate.

EXAMPLE 282.PREPA'RATION 0F a-FURYL METHYL KETONE The reaction between 1 mole of u-furylmagnesium chloride-tetrahydrofuran complex, 0.5 mole of zinc chloride, and 1 mole of acetyl chloride by the process of Example 29 gives as the final product a -furyl methyl ketone.

EXAMPLE 233.-PREPARATION 0E a-FURYL PI-IENYL KETONE The conditions of Example 29 are 'followed, using equimolar quantities of ot-furylmagnesium chloride-tetrahydro-furan complex and benzoyl chloride as reactants in the presence of zinc chloride. The resulting product is a-furyl phenyl ketone.

EXAMPLE 234.PREPARATION OF DI (wFUIiOYL) Two moles of a-furylmagnesium chloride-tetrahydrofuran complex react with 1 mole of oxalyl chloride (zinc chloride present) under the conditions of Example 29 to yield di-(a-furoyl).

EXAMPLE 235.-PREPARATION OF ETH'YL 84a- FUROYL) PROPIONATE When equimolar quantities of a-furylmagnesium chloride-tetrahydrofuran complex and the acid chloride of monoethyl succinate are allowed to react according to Example 29 (zinc chloride present), there is obtained ethyl fi-(oz-furyl) propionate.

EXAMPLE 236.PREPA'RATION OF cr-FURYL METHYL KETONE Equimolar quantities of a-furylmagnesium chloridetetrahydrofuran complex and acetonitrile are allowed'to react by the procedure of Example 5. The product thus obtained is u-furyl methyl ketone.

EXMHELE 2am+=i=nnmimmron on m a-nnnrm r:

J' KETONE w The reaction between limole of 'a-furylmagnesium chloride-tetrahydrofuran complex, 0.5 mole of zinc chlor ide, and hl mole of furoyl chloride in the manner described in Example 29 leads to.di(a-furyl) ketone.

EXAMPLE 238.PREPARATION OF tX-FURYL PHENYL V I KETONE One mole of u-furylmagnesium chloride-tetrahydrofuran complex reacts with 1 mole of benzonitrile under the conditions of Example 6 to yield u-furyl phenyl ketone.

EXAMPLE 239.--PREPARATION OF 5-CHLORO-2- THIOPHENEALDEHYDE One mole of S-chloro-Z-thienylmagnesium chloridetetrahydrofuran complex is added to a stirred solution of 4 moles of methyl formate in tetrahydrofuran in the manner described in Example 4. From the organic layer there is obtained 5-chloro-Z-thiophenealdehyde.

EXAMPLE Wills-PREPARATION OF DI(5 -CHLORO- 2-l I THIENYMCAR'BINOII When 1 moleof methyl formate is added to 2 moles of S-chloro -'2 thienylmagnesium chloride tetrahydrofuran complex under, the conditions of Example 6, the resulting product is di(5-chloro 2-thienyl)carbinol; I

EXAMPLE 241.--PREPARATION F DI(-CHLORO-2 THIENYMMETHYLCA'RBINOL Two moles of 5-chloro-2-thienylmagnesium chloridetetrahydrofuran complex are allowed to react with 1 mole of ethyl acetate using the procedure of Example 5. The product thus obtained is di(5-chloro-2-tl1ienyl)methylcarbinol.

EXAMPLE 242.-PREPARATION OF ETHYL Dus- CHLORO-Z-THIENYL)-HYDROXYACETATE The reaction between 2 moles of 5-chloro-2-thienylmagnesium chloride-tetrahydrofuran complex andfl mole of diethyl oxalate by the method of Example 6 yields ethyl di(5-ch1oro-2-thienyl)hydroxyacetate. EXAMPLE 243.--PREPARATION OF 1,1,10,10-TE'1RAw CHLQRO-Z'THIENYL)-1,10DIHYDROXYDECANE When 4 moles of S-chloro-2-thienylmagnesium chloride-tetrahydrofuran complex are allowed to reactwith 1 mole of diethyl, sebacate under the conditions of Example 5, there is obtained 1,l',l0,l0-tetra(5-chloro-2- thienyl)-1,l0-dihydroxydecane.

EXAMPLE 244.PREPARATION on ea l-lmto-cnnono- 2-THIENYL)-4HYDROXYBUTYRATE -Threemoles of 5 chloro-2-thienylmagnesium chloridetetrahydrofuran complex add to 1 mole of diethyl maleate under the conditions of Example 5 to give 3,4,4-tri(5- chloro-2-thienyl)4-hydroxybutyrate.

EXAMPLE 245.-PREPARATION on DI(5-CHLORO-2- THIENYMPHENYLCARBINOL Thereactionbetween 2 moles of 5-chloro-2-thienylmagnesium chloride-tetrahydrofuran complex and 1 mole of methyl benzoate is carried out in the manner described in Example 6. From the organic layer there is isolated.

di (S-chloroQ-thienyl) phenylcarbinol.

EXAMPLE 24'6.--PREPARATION 0F DI- 5-CHLoR0-2 THIENYL) a-FURYLCARBINOL When 2 moles of 5-chloro-2-thienylmagnesium chloridetetrahydrofuran complex are caused to react with 1 mole of methyl furoate by the procedure of Example 5, there is obtained di (5-.chloro2-thienyl) a-furylcarbinol.

38 EXAMPLE 248.4-1REPARATION 0F METHYL 445-" CHLORO-2-THIENYL) -4-HYDROXYVALERATE Equimolar quantities of 5-chloro-2-thienylmagnesium chloride-tetrahydrofuran complex and methyl levulinate are allowed to react by the procedure of Example 5 to give methyl 4-(5-chloro-2-thienyl)-4-hydroxyvalerate.

EXAMPLE 249.--PREPARATION OF s-cnLoao- THIENYL METHYL KETONE The reaction between 1 mole of S-chloro-Z-thienylmagnesium chloride-tetrahydrofuran complex, 0.5 mole of the zinc chloride, and 1 mole of acetyl chloride'by the process of Example 29 gives as the final product S-chloro-Z-thienyl methyl ketone.

EXAMPLE 250.- -PREPARATION 0F S-CHLORO-Z- v THIENYL PHENYL KETONE The conditions of Example 29 are followed, using equimolar quantities of 5-chloro-2-thienylmagnesium chloride-tetrahydrofuran complex and benzoyl chloride as reactants in the presence of Zinc chloride. The resulting product is S-chloro-Z-thienyl phenyl ketone. 2 EXAMPLE 251.PREPARATION 0F DI(5-CHLOR0-2- V THENOYL) Two moles" of S-chloro-Z-thienylmagnesium chloridetetrahydrofuran complex react 'with 1 mole of oxalyl chloride(zinc chloride present) under the conditions of Example 29 to yield di(5-chloro-2-thenoyl). V EXAMPLE 252,-PREPARA'1ION OF ETHYL 45- CHLORO-Z-THENOYL)PROPIONATE Whenequimolar quanities of 5-chloro-2-thienyl1riag nesium chloride-tetrahydrofuran complex and the acid chloride of monoethyl succinate are allowed to react according to Example 29 (zinc chloride present), there Y is obtained ethyl fl-(S-chloro-Z-thenoyl)propionate.

EXAMPLE 253.'P=REP'ARATION on 5-crILOR0-2- THIENYL' u-FURYL KETONE -."Il1c' reaction between 1 mole of S-cihloro-Z-thienylmagnesium chloride-tetrahydrofuran complex, 0.5 mole' of zinc chloride, and 1 mole of furoyl chloride in the manner described in Example 29 leads to 5-chloro-2- thienyl u-furyl ketone.

EXAMPLE 254.PREPARATION OF 5-CHLORO-2- THIENYL METHYL KETONE Eguimolar quantities of 5-chloror2-thienylmagnesium chloride-tetrahydrofuran complex and acetonitrile are allowed to react by the procedure of Example 5. The product thus obtained is 5 -chloro-2-thieny1 methyl ketone. EXAMPLE 255 .-P REPARATION OF 5-CHLORO-2- THIENYL PHENYL KETONE v 'One 'mole of 5-chloro-2-th'ienylmagnesium chloridetetrahydrofuran complex reacts with 1 mole of benzonitrile under the conditions of Example 6 to yield 5- chloro-Z -thienyl phenyl ketone.

EXAMPLE 256.-'PREPARATION OF DI[(0-FLUORO' PHENYL) CARBINOL When l/mole of methyl formate is added to 2 moles,

EXAMPLE 258.-'PREPARATION 0F Dum-FLUono PHENYMCARBINOL The l.reaction between 2 moles of 'm-fluorophenylcomplex under the conditionsof Example 6., the resulting magnesium'chloride-tetrahydrofuran complex and 1' mole of Example 6 yields of methyl'formate by the method di(mfluorophenyl)carbinol, l

EXAMPLE 261.-PREPARATION 0F DI( -FLUOR0 PHENYL)METHYLCARBI-NOL Two moles of p-fluorophenylmagnesium chloridetetrahydrofuran complex are allowed to react with 1 mole of ethyl acetate using the procedure of Example 5. The'product thus obtained is di(p-tluorophenyDmethylcarbinol.

EXAMPLE 262. PnEPA-RATION on DI(DIFLUORO- PH-ENYL) CARBINOL When 1 mole of methyl. formate is added to 2 moles of difluorophenylmagnesium chloride-tetrahydrofuran complex under the conditions of Example 6, the resulting product is di(difluorophenyl)carbinol.

EXAMPLE 263.PREPARATIO N OF DItDIFLUORO- PHENYL)METHYLCARBINOL Two moles of difiuorophenylmagnesium chloridete'trahydrofuran complex are allowed to react with 1 mole of ethyl acetate using the procedureof Example 5. The product thus obtained is di(difiuorophenyl)methylcarbinol.

' EXAMPLE 264.PREPARATION OF DI(TRIFLUORO- PHENYL) CARBINOL The reaction between 2 moles of trifiuorophenylmagnesium chloride-tetrahydrofuran complex and 1 mole of methyl formate by the method of Example 6 yields di- (trifluorophenyl carbinol.

EXAMPLE 265..PREPARATION OF DI(TRIFLUORO- PI-IENYL) METHYLCARBINOL When 2 moles of trifiuorophenylmagnesium chloridetetrahydrofuran complex are allowed to react with 1 mole of ethyl acetate under the conditions of Example 5, there is obtained di(trifiuorophenyl) methylcarbinol.

EXAMPLE 266.P'REPA'"RATION OF DI(PENTAFLUORO- PHENYL) CARBINOL When 1 mole of methyl formate is added to 2 moles of pentafluorophenylmagnesium chloride-tetrahydrofuran complex in the manner described in Example 6, the resulting product is di(pentafiuorophenyl) carbinol.

EXAMPLE 268.PREPARATION 0E DI(2-BENZO- THIAZOLYL) METHYLCA'RBINOL The reaction of 2 moles of 2-benzothia2olylmagnesium chloride-tetrahydrofuran complex with 1 mole of ethyl acetate according to the method of Example 5 gives di(Z-benzothiazolyl) methylcarbinol.

EXAMPLE 269.PREPARATION 0F DI'(2-BENZOX- AZOLYL) METHYLCARBINOL When 2 moles of 2-benzoxazolylmagnesium chloridetetrahydrofuran complex react with '1 mole of ethylacctate by the procedure of Example 6, the resultingproduct is di(2-benzoxazolyl) methylcarbinol.

an EXAMPLE 270.PREPARATION OF DuaMntrHYL-a BENZOTHIAZOLYL) METHYLCARBINOL Two .moles of 2-methyl-5-benzothiazolylmagnesium chloride-tetrahydrofuran complex are allowed to react with 1 mole of ethyl acetate using the procedure of Example 5. The product thus obtained is di(Z-methyl-S- benzothiazolyl) methylcarbinol.

EXAMPLE 271.PREPARATION 0F DI(2-QUINOLYL) METHYLCARBINOL When 1 mole of ethyl'acetate is added to 2 moles of 2- quinolylmagnesium chloride-tetrahydrofuran complex in the manner described in Example 6, there is obtained di( Z-quinolyl -methylcarbinol.

EXAMPLE 2 72.PREPAEATION OF I)I(6-QUINOLYL) METHYLCARBINOL I The reaction of 2 moles of6-quinolyln1agnesium chloride-tetrahydrofnran complex with 1 mole of ethyl acetate according to the method of Example '5 yields. di(6- quinolyl) methylcarbinol.

EXAMPLE 273. PREPARATION 0F DUB-QUINOLYL) METHYLCARBINOL when Zmoles of 8-quinolylmagnesium chloride-tetra hydrofuran complex react with 1 mole of ethyl acetate by the procedure of Example 6, the resulting product is di(S-quinoly'l) methylcarbinol.

EXAMPLE 274.'PREPARATION 0E DI(6-CHLORO-2- METHOXY-Q-ACRIDYL) METHYLCARBINOL Two moles of 6-chloro-2-methoxy-9-acridylmagnesiu1n chloride tetrahydrofuran complex are allowed to react with 1 mole ofethyl acetate using the procedure of Example 5. The product thus obtained is di(6-chloro-2- methoxy-9-acridyl) methylcarbinol.

EXAMPLE 275.PREPARATION OF DI(4-CHLORO 6- PYRIMIDYL) METHYLCA'RBINOL When 1 mole of ethyl acetate is added to :2 moles of 4 chloro-6-pyrimidylmagnesium chloride tetrahydrofuran complex in the manner described in Example 6, there is obtained di(4-chloro-6-pyrimidyl) methylcarbinol. EXAMPLE 276.-PREPARATION OF DI(4,5,6-TRICHLOR0- 2-PYRIMIDYL) METHYLCARBINOL The reaction of 2 moles of 4,5,d-trichloro-Z-pyrimidylmagnesium chloride-tetrahydrofuran complex with 1 mole of ethyl acetate according to the method of Example 5 yields di(4,S,6-trichloro-2-pyrimidyl) methylcarbinol.

EXAMPLE 277,-PREPARATION 0F DI(4,6-IDICHLOROSZ- PYRIMIDYL) ME'lI-IYLCARBINOL When .2 moles of 4,6-dichloro-2-pyrimidylmagnesium chloride-tetrahydrofuran complex'reactwith 1 mole of ethyl acetate by the procedure of Example 6, the resulting product is di(4,6-dichloro-2-pyrimidyl) methylcarbinol.

EXAMPLE 278.-PREPARATION OF DIG-CYCLO- HEXENYL-L) METHYLCARBINOL Two moles of l-cyclohexenyl-l-magnesium chloridetetrahydrofuran complex are allowed to react with 1 mole of ethyl acetate using the procedure of Example 5. The

product thus obtained is di(l-cyclohexenyl-1-) methyl-.

carbinol.

EXAMPLE 27a.-PREPARAT:0N OF ET-HYDDHLCYCLO- HEXEN YL-1-) I-IYDROKYACETATE The reaction between 2 moles of l-cyclohexenyl-lmagnesium chloride-tetrahydrofuran complex and 1 mole of diethyl oxalate according to the method of Example 6 yields ethyl di(l-cyclohexenyhl)-hydroxyacctatc.

EXAMPLE 280.';-PREPARATION OF DI(k-MIJTIIIYL- PENTEN-LYL-2) METIIYLCARBIN 0L .When 1 mole of ethyl acetate is added to 2 moles of 4- methylpenten-I-yI-Z-magnesium chloride-tetrahydrofuran complex in the vmanner described in Example-6, there is obtained di( 4-methylpentenl-yl-2) -methylcarbinol. 

1. A PROCESS COMPRISING REACTING AN ACID DERIVATIVE SELECTED FROM THE CLASS CONSISTING OF ETHYL MALONATE, ETHYL SUCCINATE, ETHYL PHTHALATE, METHYL FORMATE, ETHYL ACETATE, BUTYL LAURATE, METHYL OLEATE, DIETHYL OXALATE, DIBUTYL SUCCINATE. DIMETHYL ADIPATE, DIMETHYL SEBACATE, DIETHYL ANISATE, ATE, DIETHYL TEREPHTHALATE, METHYL BENZOATE, METHYL ANISATE, METHYL FUROATE, METHYL NICOTINATE, BUTY 2,4-DICHLOROPHENOXYACETATE, METHYL, LEVULINATE, MONOETHYL, SUCCINATE DIETHYL SEBACATE, ETHYL PERFLUOROBUTYRATE, ETHYL PERFLUOROCAPRATE, ETHYL TRICHLOROACETATE, DIOCTYL OXALATE, ETHYL TRIFLUOROACETATE, BUTYL ACETATE, METHYL ACRYLATE, ACETYL CHLORIDE, BUTYRYL CHLORIDE, BENZOYL CHLORIDE, OXALYL CHLORIDE, ADIPOYL DICHLORIDE, FUROYL CHLORIDE, ACETONITRILE, BUTYRONITRILE, BENZONITRILE, ACRYLONITRILE AND FUMARONITRIE, WITH AN ORGANOMAGNESUIM CHLORIDE, IN THE PRESENCE OF COMPONND Q; SAID ORGANOMAGNESUIM CHLORIDE, BEING PREPARED BY REACTING AN ORGANIC CHLORIDE OF THE FORMULA RCI WHEREIN R IS SELECTED FROM THE CLASS CONSISTING OF ARYL, VINYL AND AROMATIC-HETEROCYCLIC RADICALS, WITH MAGNESIUM IN COMPOUND Q; WHEREIN SAID COMPOUND Q IS SELECTED FROM THE CLASS CONSISTING OF TETRAHYDROFURAN, TETRAHYDROPYRAN, 2-ETHOXY-TETRAHYDROPYRAN, SIHYDROPYRAN, TETRAHYDRO FURFURYL ETHYL ETHER AND 2-METHYL TETRAHYDROFURAN; WHEREIN SAID AROMATIC-HETEROCYCLIC RADICAL IS SELECTED FROM THE CLASS CONSISTING OF 2-THIENYL. 2-PYRIDYL, A-FURYL, 5CHLORO-2-THIENYL, 2 - NEBZOTHIAZOLY, 2 - BENZOXAZOLYL, 2METHYL-5-BENZOSTHUAZOLYL, 2-QUINOLYL, 6-QUINOLYL, 8-QUINOLYL, 6-CHLORO-2-METHOXY-9-ACRIDYL, 6-PYRIMIDYL, 4,5,6TRICHLORO-2-PYRIMIDYL, 4,6-DICHLORO-2-PYRIMIDYL AND NMETHYLPYRRYL.
 2. THE PROCESS ACCORDING TO CLAIM 1 IN WHICH R IS THE VINYL RADICAL. 